Method and catalyst system for preparing polymers and block copolymers

ABSTRACT

The present invention provides methods for producing block copolymers, either by the sequential addition of monomers, or using a “one-pot” method. The invention also relates to novel methods for producing polyesters by ring opening lactides and/or lactones and by copolymerising anhydrides and epoxides.

FIELD OF THE INVENTION

The present invention relates to methods for producing block copolymers,either by the sequential addition of monomers, or using a “one-pot”method. In particular, the chemistry of the catalyst active site allowsselective polymerisation of particular monomers and control of blocksequence in the production of block copolymers comprising polycarbonateblocks and polyester blocks, using a single catalytic system. It ispossible to switch between the formation of a polyester and apolycarbonate by controlling the growing polymer chain end and byselecting the identity and amount of the monomers used. The methodsdescribed allow the product of the preparation of di-block copolymers,as well as more complex block sequences, including ABA and ABC typeblock copolymers. The invention also relates to novel methods forproducing polyesters by ring opening lactides and/or lactones and bycopolymerising anhydrides and epoxides.

BACKGROUND

Block copolymers are polymers having two or more distinct polymericunits, or “blocks”. Such polymers are useful in a variety of differentapplications, and it is particularly preferred to be able to produceblock copolymers having polyester and polycarbonate blocks.

Block copolymers can be produced in a variety of different ways. Forexample, the individual blocks may be prepared separately, and thenjoined together. Alternatively, a first block, comprising an initiatingmoiety (also known as a “macroinitiator”) can be added to a mixture ofone or monomers, and the second block is grown from the end of thepre-formed block. However, such methods require the formation andpurification of the first blocks prior to the formation of a secondblock, and generally involve the use of different catalytic systems toproduce each block. These methods can therefore be costly and difficultto use.

The inventors have surprisingly found that it is possible to produceblock copolymers comprising two or more blocks, using a single catalyticsystem, either by the subsequent addition of monomer, or by a “one-pot”method in which all of the monomers are present in the reaction mixtureat the start of the reaction.

SUMMARY OF THE INVENTION

In a first aspect, the present invention provides a method for preparinga block copolymer, using a single catalytic system, wherein the singlecatalytic system comprises a catalyst of formula (I):

Wherein:

[M] is a metal complex having at least one metal atom M coordinated by aligand system;

M is Zn, Cr, Co, Mn, Mg, Fe, Ti, Ca, Ge, Al, Mo, W, Ru, Ni or V;

Z is absent, or is independently selected from -E-, -EX(E)-, or-EX(E)E-, each E is independently selected from O, S or NR^(Z), whereinR^(Z) is H, or optionally substituted aliphatic, heteroaliphatic,alicyclic, heteroalicyclic, aryl, heteroaryl, alkylaryl oralkylheteroaryl;

X is C or S

R is hydrogen, or optionally substituted aliphatic, heteroaliphatic,alicyclic, heteroalicyclic, aryl, heteroaryl, alkylaryl,alkylheteroaryl, silyl or a polymer; and when Z is absent, R mayadditionally be selected from halide, phosphinate, azide and nitrate;

the method comprising the steps of:

-   -   a) forming a first block by polymerising a first monomer or        combination of monomers selected from the groups (i) to (iii):        -   Group (i): a lactide and/or a lactone,        -   Group (ii): an epoxide and an anhydride, or        -   Group (iii): an epoxide and carbon dioxide,    -   b) optionally contacting the catalyst of formula (I) with a        compound [Y] which is capable converting the group —Z—R, wherein        Z is absent or a group selected from -E-X(E)- or -E-X(E)E-, to a        group —Z—R wherein Z is -E-;    -   c) forming a second block by polymerising a second monomer or        combination of monomers selected from a different group (i)        to (iii) to that selected for the first monomer or combination        of monomers:        -   Group (i): a lactide and/or a lactone,        -   Group (ii): an epoxide and an anhydride, or        -   Group (iii): an epoxide and carbon dioxide,

wherein when the first monomer or combination of monomers is Group (i),Z is -E-; and

wherein when the first monomer or combination of monomers is Group (ii)or Group (iii),

and the second monomer or combination of monomers is Group (i), step b)is performed after step a).

In a second aspect, the present invention provides a method forproducing a block copolymer, said block copolymer having a first andsecond block, using a single catalytic system, wherein the singlecatalytic system comprises a catalyst of formula (I):

Wherein:

[M] is a metal complex having at least one metal atom M coordinated by aligand system;

M is Zn, Cr, Co, Mn, Mg, Fe, Ti, Ca, Ge, Al, Mo, W, Ru, Ni or V;

Z is absent, or is independently selected from -E-, -EX(E)-, or-EX(E)E-,

each E is independently selected from O, S or NR^(Z), wherein R^(Z) isH, or optionally substituted aliphatic, heteroaliphatic, alicyclic,heteroalicyclic, aryl, heteroaryl, alkylaryl or alkylheteroaryl;

X is C or S

R is hydrogen, or optionally substituted aliphatic, heteroaliphatic,alicyclic, heteroalicyclic, aryl, heteroaryl, alkylaryl,alkylheteroaryl, silyl or a polymer; and when Z is absent, R may also beselected from halide, phosphinate, azide and nitrate;

the method comprising the steps of:

-   -   a) providing a mixture comprising:        -   I. an epoxide;        -   II. a first monomer or combination of monomers selected from            a group (i) to (iii):            -   Monomer (i): a lactide and/or a lactone,            -   Monomer (ii): an anhydride, or            -   Monomer (iii): carbon dioxide, and        -   III. a second monomer or combination of monomers selected            from a different group (i) to (iii) to that selected for the            first monomer or combination of monomers:            -   Monomer (i): a lactide and/or a lactone,            -   Monomer (ii): an anhydride, or            -   Monomer (iii): carbon dioxide; and    -   b) contacting the mixture with the single catalytic system;

wherein the rate of insertion of the first monomer or combination ofmonomers into the bond between the metal complex [M] and the ligand —Z—Ris faster than the rate of insertion of the second monomer orcombination of monomers into the bond between the metal complex [M] andthe ligand —Z—R;

wherein when the first monomer or combination of monomers is Group (i),either —Z—R is -E-R, or the mixture comprises a compound [Y]; and

wherein when the second monomer or combination of monomers is Group (i),the mixture comprises a compound [Y].

In a third aspect, the present invention provides a method for producinga polyester, comprising contacting a lactone and/or a lactide with acatalyst system having a catalyst of formula (IA):

wherein

R₁ and R₂ are independently hydrogen, halide, a nitro group, a nitrilegroup, an imine, an amine, an ether group, a silyl ether group, athioether group, a sulfoxide group, a sulfinate group, or an acetylidegroup or an optionally substituted alkyl, alkenyl, alkynyl, haloalkyl,aryl, heteroaryl, alicyclic or heteroalicyclic;

R₃ is optionally substituted alkylene, alkenylene, alkynylene,heteroalkylene, heteroalkenylene, heteroalkynylene, arylene,heteroarylene or cycloalkylene, wherein alkylene, alkenylene,alkynylene, heteroalkylene, heteroalkenylene and heteroalkynylene mayoptionally be interrupted by aryl, heteroaryl, alicyclic orheteroalicyclic;

R₄ is H, or optionally substituted aliphatic, heteroaliphatic,alicyclic, heteroalicyclic, aryl, heteroaryl, alkylheteroaryl oralkylaryl;

R₅ is H, or optionally substituted aliphatic, heteroaliphatic,alicyclic, heteroalicyclic, aryl, heteroaryl, alkylheteroaryl oralkylaryl;

E₁ is C, E₂ is O, S or NH or E₁ is N and E₂ is O;

R is hydrogen, or optionally substituted aliphatic, heteroaliphatic,alicyclic, heteroalicyclic, aryl, heteroaryl, alkylaryl, alkylheteroarylsilyl, or a polymer;

Z is -E-;

E is —O—, —S—, or NR^(Z), wherein is H, or optionally substitutedaliphatic, heteroaliphatic, alicyclic, heteroalicyclic, aryl,heteroaryl, alkylaryl or alkylheteroaryl;

each G is independently absent or a neutral or anionic donor ligandwhich is a Lewis base; and

M is Zn(II), Cr(II), Co(II), Mn(II), Mg(II), Fe(II), Ti(II),Cr(III)-Z—R, Co(III)Z—R, Mn (III)-Z—R, Fe(III)-Z—R, Ca(II), Ge(II),Al(III)-Z—R, Ti(III)-Z—R, V(III)-Z—R, Ge(IV)-(—Z—R)₂ or Ti(IV)-(—Z—R)₂.

In a fourth aspect of the invention, there is provided method forproducing a polyester, comprising contacting an anhydride and an epoxidewith a catalyst system having a catalyst of formula (IA):

wherein

R₁ and R₂ are independently hydrogen, halide, a nitro group, a nitrilegroup, an imine, an amine, an ether group, a silyl ether group, athioether group, a sulfoxide group, a sulfinate group, or an acetylidegroup or an optionally substituted alkyl, alkenyl, alkynyl, haloalkyl,aryl, heteroaryl, alicyclic or heteroalicyclic;

R₃ is optionally substituted alkylene, alkenylene, alkynylene,heteroalkylene, heteroalkenylene, heteroalkynylene, arylene,heteroarylene or cycloalkylene, wherein alkylene, alkenylene,alkynylene, heteroalkylene, heteroalkenylene and heteroalkynylene mayoptionally be interrupted by aryl, heteroaryl, alicyclic orheteroalicyclic;

R₄ is H, or optionally substituted aliphatic, heteroaliphatic,alicyclic, heteroalicyclic, aryl, heteroaryl, alkylheteroaryl oralkylaryl;

R₅ is H, or optionally substituted aliphatic, heteroaliphatic,alicyclic, heteroalicyclic, aryl, heteroaryl, alkylheteroaryl oralkylaryl;

E₁ is C, E₂ is O, S or NH or E₁ is N and E₂ is O;

Z is absent, or is selected from -E-, -EX(E)-, or -EX(E)E-;

X is S or C;

E is —O—, —S—, or NR^(Z), wherein is H, or optionally substitutedaliphatic, heteroaliphatic, alicyclic, heteroalicyclic, aryl,heteroaryl, alkylaryl or alkylheteroaryl;

R is hydrogen, or optionally substituted aliphatic, heteroaliphatic,alicyclic, heteroalicyclic, aryl, heteroaryl, alkylaryl,alkylheteroaryl, or silyl, or a polymer; and when Z is absent, R mayadditional be selected from halide, phosphinate, azide and nitrate;

each G is independently absent or a neutral or anionic donor ligandwhich is a Lewis base; and

M is Zn(II), Cr(II), Co(II), Mn(II), Mg(II), Fe(II), Ti(II),Cr(III)-Z—R, Co(III)-Z—R, Mn (III)-Z—R, Fe(III)-Z—R, Ca(II), Ge(II),Al(III)-Z—R, Ti(III)-Z—R, V(III)-Z—R, Ge(IV)-(—Z—R)₂ or Ti(IV)-(—Z—R)₂.

In a fifth aspect of the invention, there is provided a polymerobtainable from the method according to any of the first, second, thirdor fourth aspects of the invention.

Definitions

For the purpose of the present invention, an aliphatic group is ahydrocarbon moiety that may be straight chain or branched and may becompletely saturated, or contain one or more units of unsaturation, butwhich is not aromatic. The term “unsaturated” means a moiety that hasone or more double and/or triple bonds. The term “aliphatic” istherefore intended to encompass alkyl, alkenyl or alkynyl groups, andcombinations thereof. An aliphatic group is preferably a C₁₋₂₀aliphaticgroup, that is an aliphatic group with 1, 2, 3, 4, 5, 6, 7, 8, 9, 10,11, 12, 13, 14, 15, 16, 17, 18, 19 or 20 carbon atoms. Preferably, analiphatic group is a C₁₋₁₅aliphatic, more preferably a C₁₋₁₂aliphatic,more preferably a C₁₋₁₀aliphatic, even more preferably a C₁₋₈aliphatic,such as a C₁₋₆aliphatic group.

An alkyl group is preferably a “C₁₋₂₀ alkyl group”, that is an alkylgroup that is a straight or branched chain with 1 to 20 carbons. Thealkyl group therefore has 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14,15, 16, 17, 18, 19 or 20 carbon atoms. Preferably, an alkyl group is aC₁₋₁₅alkyl, preferably a C₁₋₁₂alkyl, more preferably a C₁₋₁₀alkyl, evenmore preferably a C₁₋₈alkyl, even more preferably a C₁₋₆alkyl group. Incertain embodiments, an alkyl group is a “C₁₋₆ alkyl group”, that is analkyl group that is a straight or branched chain with 1 to 6 carbons.The alkyl group therefore has 1, 2, 3, 4, 5 or 6 carbon atoms.Specifically, examples of “C₁₋₂₀ alkyl group” include methyl group,ethyl group, n-propyl group, iso-propyl group, n-butyl group, iso-butylgroup, sec-butyl group, tert-butyl group, n-pentyl group, n-hexyl group,n-heptyl group, n-octyl group, n-nonyl group, n-decyl group, n-undecylgroup, n-dodecyl group, n-tridecyl group, n-tetradecyl group,n-pentadecyl group, n-hexadecyl group, n-heptadecyl group, n-octadecylgroup, n-nonadecyl group, n-eicosyl group, 1,1-dimethylpropyl group,1,2-dimethylpropyl group, 2,2-dimethylpropyl group, 1-ethylpropyl group,n-hexyl group, 1-ethyl-2-methylpropyl group, 1,1,2-trimethylpropylgroup, 1-ethylbutyl group, 1-methylbutyl group, 2-methylbutyl group,1,1-dimethylbutyl group, 1,2-dimethylbutyl group, 2,2-dimethylbutylgroup, 1,3-dimethylbutyl group, 2,3-dimethylbutyl group, 2-ethylbutylgroup, 2-methylpentyl group, 3-methylpentyl group and the like. Alkenyland alkynyl groups are preferably “C₂₋₂₀alkenyl” and “C₂₋₂₀alkynyl”respectively, that is an alkenyl or alkynyl group which is a straightchain or branched chain with 2 to 20 carbons. The alkenyl or alkynylgroup therefore has 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16,17, 18, 19 or 20 carbon atoms. Preferably, an alkenyl group or analkynyl group is “C₂₋₁₅alkenyl” and “C₂₋₁₅alkynyl”, more preferably“C₂₋₁₂alkenyl” and “C₂₋₁₂alkynyl”, even more preferably “C₂₋₁₀alkenyl”and “C₂₋₁₀alkynyl”, even more preferably “C₂₋₈alkenyl” and“C₂₋₈alkynyl”, most preferably “C₂₋₆alkenyl” and “C₂₋₆alkynyl” groupsrespectively.

A heteroaliphatic group is an aliphatic group as described above, whichadditionally contains one or more heteroatoms. Heteroaliphatic groupstherefore preferably contain from 2 to 21 atoms, preferably from 2 to 16atoms, more preferably from 2 to 13 atoms, more preferably from 2 to 11atoms, more preferably from 2 to 9 atoms, even more preferably from 2 to7 atoms, wherein at least one atom is a carbon atom. Particularlypreferred heteroatoms are selected from O, S, N, P and Si. Whenheteroaliphatic groups have two or more heteroatoms, the heteroatoms maybe the same or different.

An alicyclic group is a saturated or partially unsaturated cyclicaliphatic monocyclic or polycyclic (including fused, bridging andspiro-fused) ring system which has from 3 to 20 carbon atoms, that is analicyclic group with 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16,17, 18, 19 or 20 carbon atoms. Preferably, an alicyclic group has from 3to 15, more preferably from 3 to 12, even more preferably from 3 to 10 ,even more preferably from 3 to 8 carbon atoms. The term “alicyclic”encompasses cycloalkyl, cycloalkenyl and cycloalkynyl groups. It will beappreciated that the alicyclic group may comprise an alicyclic ringbearing one or more linking or non-linking alkyl substitutents, such as—CH₂-cyclohexyl.

Cycloalkyl, cycloalkenyl and cycloalkynyl groups have from 3 to 20carbon atoms. The cycloalkyl, cycloalkenyl and cycloalkynyl groupstherefore have 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18,19 or 20 carbon atoms. Cycloalkyl, cycloalkenyl and cycloalkynyl groupspreferably have from 3 to 15, more preferably from 3 to 12, even morepreferably from 3 to 10, even more preferably from 3 to 8 carbon atoms.When an alicyclic group has from 3 to 8 carbon atoms, this means thatthe alicyclic group has 3, 4, 5, 6, 7 or 8 carbon atoms. Specifically,examples of the C₃₋₂₀ cycloalkyl group include cyclopropyl, cyclobutyl,cyclopentyl, cyclohexyl, cycloheptyl, adamantyl and cyclooctyl.

A heteroalicyclic group is an alicyclic group as defined above whichhas, in addition to carbon atoms, one or more ring heteroatoms, whichare preferably selected from O, S, N, P and Si. Heteroalicyclic groupspreferably contain from one to four heteroatoms, which may be the sameor different. Heterocyclic groups preferably contain from 4 to 20 atoms,more preferably from 4 to 14 atoms, even more preferably from 4 to 12atoms.

An aryl group is a monocyclic or polycyclic ring system having from 5 to20 carbon atoms. An aryl group is preferably a “C₆₋₁₂ aryl group” and isan aryl group constituted by 6, 7, 8, 9, 10, 11 or 12 carbon atoms andincludes condensed ring groups such as monocyclic ring group, orbicyclic ring group and the like. Specifically, examples of “C₆₋₁₀ arylgroup” include phenyl group, biphenyl group, indenyl group, naphthylgroup or azulenyl group and the like. It should be noted that condensedrings such as indan and tetrahydro naphthalene are also included in thearyl group.

A heteroaryl group is an aryl group having, in addition to carbon atoms,from one to four ring heteroatoms which are preferably selected from O,S, N, P and Si. A heteroaryl group preferably has from 5 to 20, morepreferably from 5 to 14 ring atoms. Specifically, examples of aheteroaryl group includes pyridine, imidazole, N-methylimidazole and4-dimethylaminopyridine.

Examples of alicyclic, heteroalicyclic, aryl and heteroaryl groupsinclude but are not limited to cyclohexyl, phenyl, acridine,benzimidazole, benzofuran, benzothiophene, benzoxazole, benzothiazole,carbazole, cinnoline, dioxin, dioxane, dioxolane, dithiane, dithiazine,dithiazole, dithiolane, furan, imidazole, imidazoline, imidazolidine,indole, indoline, indolizine, indazole, isoindole, isoquinoline,isoxazole, isothiazole, morpholine, napthyridine, oxazole, oxadiazole,oxathiazole, oxathiazolidine, oxazine, oxadiazine, phenazine,phenothiazine, phenoxazine, phthalazine, piperazine, piperidine,pteridine, purine, pyran, pyrazine, pyrazole, pyrazoline, pyrazolidine,pyridazine, pyridine, pyrimidine, pyrrole, pyrrolidine, pyrroline,quinoline, quinoxaline, quinazoline, quinolizine, tetrahydrofuran,tetrazine, tetrazole, thiophene, thiadiazine, thiadiazole, thiatriazole,thiazine, thiazole, thiomorpholine, thianaphthalene, thiopyran,triazine, triazole, and trithiane.

The term “halide” or “halogen” are used interchangeably and, as usedherein mean a fluorine atom, a chlorine atom, a bromine atom, an iodineatom and the like, preferably a fluorine atom, a bromine atom or achlorine atom, and more preferably a fluorine atom or a bromine atom.

A haloalkyl group is preferably a “C₁₋₂₀ haloalkyl group”, morepreferably a “C₁₋₁₅ haloalkyl group”, more preferably a “C₁₋₁₂ haloalkylgroup”, more preferably a “C₁₋₁₀ haloalkyl group”, even more preferablya “C₁₋₈ haloalkyl group”, even more preferably a “C₁₋₆ haloalkyl group”and is a C₁₋₂₀ alkyl, a C₁₋₁₅ alkyl, a C₁₋₁₂ alkyl, a C₁₋₁₀ alkyl, aC₁₋₈ alkyl, or a C₁₋₆ alkyl group, respectively, as described abovesubstituted with at least one halogen atom, preferably 1, 2 or 3 halogenatom(s). Specifically, examples of “C₁₋₂₀ haloalkyl group” includefluoromethyl group, difluoromethyl group, trifluoromethyl group,fluoroethyl group, difluroethyl group, trifluoroethyl group,chloromethyl group, bromomethyl group, iodomethyl group and the like.

An alkoxy group is preferably a “C₁₋₂₀ alkoxy group”, more preferably a“C₁₋₁₅ alkoxy group”, more preferably a “C₁₋₁₂ alkoxy group”, morepreferably a “C₁₋₁₀ alkoxy group”, even more preferably a “C₁₋₈ alkoxygroup”, even more preferably a “C₁₋₆ alkoxy group” and is an oxy groupthat is bonded to the previously defined C₁₋₂₀ alkyl, C₁₋₁₅ alkyl, C₁₋₁₂alkyl, C₁₋₁₀ alkyl, C₁₋₈ alkyl, or C₁₋₆ alkyl group respectively.Specifically, examples of “C₁₋₂₀alkoxy group” include methoxy group,ethoxy group, n-propoxy group, iso-propoxy group, n-butoxy group,iso-butoxy group, sec-butoxy group, tert-butoxy group, n-pentyloxygroup, iso-pentyloxy group, sec-pentyloxy group, n-hexyloxy group,iso-hexyloxy group, n-hexyloxy group, n-heptyloxy group, n-octyloxygroup, n-nonyloxy group, n-decyloxy group, n-undecyloxy group,n-dodecyloxy group, n-tridecyloxy group, n-tetradecyloxy group,n-pentadecyloxy group, n-hexadecyloxy group, n-heptadecyloxy group,n-octadecyloxy group, n-nonadecyloxy group, n-eicosyloxy group,1,1-dimethylpropoxy group, 1,2-dimethylpropoxy group,2,2-dimethylpropoxy group, 2-methylbutoxy group, 1-ethyl-2-methylpropoxygroup, 1,1,2-trimethylpropoxy group, 1,1-dimethylbutoxy group,1,2-dimethylbutoxy group, 2,2-dimethylbutoxy group, 2,3-dimethylbutoxygroup, 1,3-dimethylbutoxy group, 2-ethylbutoxy group, 2-methylpentyloxygroup, 3-methylpentyloxy group and the like.

An alkylthio group is preferably a “C₁₋₂₀ alkylthio group”, morepreferably a “C₁₋₁₅ alkylthio group”, more preferably a “C₁₋₁₂ alkylthiogroup”, more preferably a “C₁₋₁₀ alkylthio group”, even more preferablya “C₁₋₈ alkylthio group”, even more preferably a “C₁₋₆ alkylthio group”and is a thio (—S—) group that is bonded to the previously defined C₁₋₂₀alkyl, C₁₋₁₅ alkyl, C₁₋₁₂ alkyl, C₁₋₁₀ alkyl, C₁₋₅ alkyl, or C₁₋₆ alkylgroup respectively.

An alkylaryl group can comprise any of the alkyl or aryl groupsdiscussed above. Preferably the alkylaryl group is a “C₆₋₁₂ aryl C₁₋₂₀alkyl group”, more preferably a preferably a “C₆₋₁₂ aryl C₁₋₁₆ alkylgroup”, even more preferably a “C₆₋₁₂ aryl C₁₋₆ alkyl group” and is anaryl group as defined above bonded at any position to an alkyl group asdefined above. The point of attachment of the alkylaryl group to amolecule may be via the alkyl portion and thus, preferably, thealkylaryl group is —CH₂-Ph or —CH₂CH₂-Ph. An alkylaryl group can also bereferred to as “aralkyl”.

An alkylheteroaryl group can comprise any of the alkyl or heteroarylgroups discussed above. Preferably the alkylheteroaryl group is a“heteroaryl C₁₋₂₀ alkyl group”, more preferably a preferably a“heteroaryl C₁₋₁₆ alkyl group”, even more preferably a “heteroaryl C₁₋₆alkyl group” and is a heteroaryl group as defined above bonded at anyposition to an alkyl group as defined above. The point of attachment ofthe alkylheteroaryl group to a molecule may be via the alkyl portion. Analkylheteroaryl group can also be referred to as “heteroaralkyl”.

An ether group is preferably a group OR₆ wherein R₆ can be an aliphatic,heteroaliphatic, alicyclic, heteroalicyclic, aryl or heteroaryl group asdefined above. In certain embodiments, R₆ can be an unsubstitutedaliphatic, alicyclic or aryl. Preferably, R₆ is an alkyl group selectedfrom methyl, ethyl or propyl. A thioether group is preferably a groupSR₆ wherein R₆ is as defined above.

A silyl group is preferably a group —Si(R₇)₃, wherein each R₇ can beindependently an aliphatic, heteroaliphatic, alicyclic, heteroalicyclic,aryl or heteroaryl group as defined above. In certain embodiments, eachR₇ is independently an unsubstituted aliphatic, alicyclic or aryl.Preferably, each R₇ is an alkyl group selected from methyl, ethyl orpropyl.

A silyl ether group is preferably a group OSi(R₈)₃ wherein each R₈ canbe independently an aliphatic, heteroaliphatic, alicyclic,heteroalicyclic, aryl or heteroaryl group as defined above. In certainembodiments, each R₈ can be independently an unsubstituted aliphatic,alicyclic or aryl. Preferably, each R₈ is an alkyl group selected frommethyl, ethyl or propyl.

A nitrile group is a group CN.

An azide group is a group —N₃.

An imine group is a group —CRNR, preferably a group —CHNR₉ wherein R₉ isan aliphatic, heteroaliphatic, alicyclic, heteroalicyclic, aryl orheteroaryl group as defined above. In certain embodiments, R₉ isunsubstituted aliphatic, alicyclic or aryl. Preferably R₉ is an alkylgroup selected from methyl, ethyl or propyl.

An acetylide group contains a triple bond —C≡C—R₁₀, preferably whereinR₁₀ can be an aliphatic, heteroaliphatic, alicyclic, heteroalicyclic,aryl or heteroaryl group as defined above. For the purposes of theinvention when R₁₀ is alkyl, the triple bond can be present at anyposition along the alkyl chain. In certain embodiments, R₁₀ isunsubstituted aliphatic, alicyclic or aryl. Preferably R₁₀ is methyl,ethyl, propyl or phenyl.

An amino group is preferably —NH₂, —NHR₁₁ or —N(R₁₁)₂ wherein R₁₁ can bean aliphatic, heteroaliphatic, alicyclic, heteroalicyclic, a silylalkyl,aryl or heteroaryl group as defined above. It will be appreciated thatwhen the amino group is N(R₁₁)₂, each R₁₁ group can be independentlyselected from an aliphatic, heteroaliphatic, alicyclic, heteroalicyclica silylalkyl group, heteroaryl or an aryl group as defined above. Incertain embodiments, each R₁₁ is independently an unsubstitutedaliphatic, alicyclic or aryl. Preferably R₁₁ is methyl, ethyl, propyl,SiMe₃ or phenyl. Where W of the chain transfer agent is amine, the amineis preferably NH₂ or NHR₁₁.

An alkylamino group may be a group —NHR₁₁ or —N(R₁₁)₂ as defined above.

An amido group is preferably —NR₁₂C(O)— or —C(O)—NR₁₂— wherein R₁₂ canbe hydrogen, an aliphatic, heteroaliphatic, alicyclic, heteroalicyclic,aryl or heteroaryl group as defined above. In certain embodiments, R₁₂is unsubstituted aliphatic, alicyclic or aryl. Preferably R₁₂ ishydrogen, methyl, ethyl, propyl or phenyl.

An ester group is preferably—OC(O)R₁₃— or —C(O)OR₁₃— wherein R₁₃ can behydrogen, an aliphatic, heteroaliphatic, alicyclic, heteroalicyclic,aryl or heteroaryl group as defined above. In certain embodiments, R₁₃is unsubstituted aliphatic, alicyclic or aryl. Preferably R₁₃ ishydrogen, methyl, ethyl, propyl or phenyl.

A sulfoxide is preferably —SOR₁₄, a sulfonate group is preferably—OS(O)₂R₁₄, a sulfinate group is preferably —S(O)O—R₁₄, wherein R₁₄ canbe hydrogen, an aliphatic, heteroaliphatic, alicyclic, heteroalicyclic,aryl or heteroaryl group as defined above. In certain embodiments, R₁₄is unsubstituted aliphatic, alicyclic or aryl. Preferably R₁₄ ishydrogen, methyl, ethyl, propyl or phenyl.

A carboxylate group is preferably OC(O)R₁₅, wherein R₁₅ can be hydrogen,an aliphatic, heteroaliphatic, alicyclic, heteroalicyclic, aryl orheteroaryl group as defined above. In certain embodiments, R₁₅ isunsubstituted aliphatic, alicyclic or aryl. Preferably R₁₅ is hydrogen,methyl, ethyl, propyl, butyl (for example n-butyl, isobutyl ortert-butyl), phenyl, pentafluorophenyl, pentyl, hexyl, heptyl, octyl,nonyl, decyl, undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl,hexadecyl, heptadecyl, octadecyl, nonadecyl, eicosyl, trifluoromethyl oradamantyl.

An acetamide is preferably MeC(O)N(R₁₆)₂ wherein R₁₆ can be hydrogen, analiphatic, heteroaliphatic, alicyclic, heteroalicyclic, aryl orheteroaryl group as defined above. In certain embodiments, R₁₆ isunsubstituted aliphatic, alicyclic or aryl. Preferably R₁₆ is hydrogen,methyl, ethyl, propyl or phenyl.

A phosphinate group is preferably a group —OP(O)(R₁₇)₂ wherein each R₁₇is independently selected from hydrogen, or an aliphatic,heteroaliphatic, alicyclic, heteroalicyclic, aryl or heteroaryl group asdefined above. In certain embodiments, R₁₇ is aliphatic, alicyclic oraryl, which are optionally substituted by aliphatic, alicyclic, aryl orC₁₋₆alkoxy. Preferably R₁₇ is optionally substituted aryl or C₁₋₂₀alkyl, more preferably phenyl optionally substituted by C₁₋₆alkoxy(preferably methoxy) or unsubstituted C₁₋₂₀alkyl (such as hexyl, octyl,decyl, dodecyl, tetradecyl, hexadecyl, stearyl).

It will be appreciated that where any of the above groups are present ina Lewis base G, one or more additional R^(G) groups may be present, asappropriate, to complete the valency. For example, in the context of anether an additional R^(G) group may be present to give R^(G)OR₆, whereinR^(G) is hydrogen, an optionally substituted aliphatic, heteroaliphatic,alicyclic, heteroalicyclic, aryl or heteroaryl group as defined above.Preferably, R^(G) is hydrogen or aliphatic, alicyclic or aryl.

Any of the aliphatic, heteroaliphatic, alicyclic, heteroalicyclic, aryl,heteroaryl, haloalkyl, alkoxy, alkylthio, alkylaryl, ether, ester,sulfoxide, sulfonate, sulfinate, carboxylate, silyl ether, imine,acetylide, amino, alkylamino, phosphinate or amido groups wherevermentioned in the definitions above, may optionally be substituted byhalogen, hydroxyl, nitro, carbonate, alkoxy, aryloxy, heteroaryloxy,amino, alkylamino, imine, nitrile, acetylide, or optionally substitutedaliphatic, heteroaliphatic, alicyclic, heteroalicyclic, aryl orheteroaryl groups (for example, optionally substituted by halogen,hydroxyl, nitro, carbonate, alkoxy, amino, alkylamino, imine, nitrile oracetylide).

For the purposes of all aspects of the present invention, the epoxide,anhydride, lactide and lactone substrates are not limited.

The term epoxide therefore relates to any compound comprising an epoxidemoiety. In preferred embodiments, the epoxides which are useful in thepresent invention have the following formula:

Wherein each R^(e1), R^(e2), R^(e3) and R^(e4) is independently selectedfrom hydrogen, halogen, hydroxyl, nitro, alkoxy, aryloxy, heteroaryloxy,amino, alkylamino, imine, nitrile, acetylide, carboxylate or optionallysubstituted aliphatic, heteroaliphatic, alicyclic, heteroalicyclic,aryl, heteroaryl, alkylaryl or alkylheteroaryl, or a polymeric species(e.g. polybis(phenol)A); or two or more of R^(e1), R^(e2), R^(e3) andR^(e4) can be taken together to form a saturated, partially saturated orunsaturated 3 to 12 membered, optionally substituted ring system,optionally containing one or more heteroatoms.

Preferred examples of epoxides for the purposes of the present inventioninclude propylene oxide, cyclohexene oxide, substituted cyclohexeneoxides (such as limonene oxide, C₁₀H₁₆O or2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane, C₁₁H₂₂O), alkylene oxides(such as ethylene oxide and substituted ethylene oxides), substitutedoxiranes (such as epichlorohydrin, 1,2-epoxybutane, glycidyl ethers),styrene oxide or substituted styrene oxides. For example, epoxides, mayhave the following structures:

The term anhydride relates to any compound comprising an anhydridemoiety in a ring system (i.e. a cyclic anhydride). In preferredembodiments, the anhydrides which are useful in the present inventionhave the following formula:

Wherein m″ is 1, 2, 3, 4, 5, or 6 (preferably 1 or 2), each R^(a1),R^(a2), R^(a3) and R^(a4) is independently selected from hydrogen,halogen, hydroxyl, nitro, alkoxy, aryloxy, heteroaryloxy, amino,alkylamino, imine, nitrile, acetylide, carboxylate or optionallysubstituted aliphatic, heteroaliphatic, alicyclic, heteroalicyclic,aryl, heteroaryl, alkylaryl or alkylheteroaryl, or a polymeric species(e.g. polybis(phenol)A); or two or more of R^(e1), R^(e2), R^(e3) andR^(e4) can be taken together to form a saturated, partially saturated orunsaturated 3 to 12 membered, optionally substituted ring system,optionally containing one or more heteroatoms, or can be taken togetherto form a double bond. Each Q is independently C, O, N or S, preferablyC, wherein R^(a3) and R^(a4) are either present, or absent, and

can either be ═ or —, according to the valency of Q. It will beappreciated that when Q is C, and

is ═, R^(a3) and R^(a4) (or two R^(a4) on adjacent carbon atoms) areabsent. Preferable anhydrides are set out below.

The term lactone relates to any cyclic compound comprising a —C(O)O—moiety in the ring. In preferred embodiments, the lactones which areuseful in the present invention have the following formula:

Wherein m is 1 to 20 (e.g. 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13,14, 15, 16, 17, 18, 19 or 20), preferably 2, 4, or 5; and R^(L1) andR^(L2) are independently selected from hydrogen, halogen, hydroxyl,nitro, alkoxy, aryloxy, heteroaryloxy, amino, alkylamino, imine,nitrile, acetylide, carboxylate or optionally substituted aliphatic,heteroaliphatic, alicyclic, heteroalicyclic, aryl, heteroaryl, alkylarylor alkylheteroaryl. Two or more of R^(L1) and R^(L2) can be takentogether to form a saturated, partially saturated or unsaturated 3 to 12membered, optionally substituted ring system, optionally containing oneor more heteroatoms. When m is 2 or more, the R^(L1) and R^(L2) on eachcarbon atom may be the same or different. Preferably R^(L1) and R^(L2)are selected from hydrogen or alkyl. Preferably, the lactone has thefollowing structure:

The term lactide is a cyclic compound containing two ester groups. Inpreferred embodiments, the lactides which are useful in the presentinvention have the following formula:

Wherein m′ is 1, 2, 3, 4, 5, 6, 7, 8, 9 or 10, (preferably 1 or 2, morepreferably, 1) and R^(L3) and R^(L4) are independently selected fromhydrogen, halogen, hydroxyl, nitro, alkoxy, aryloxy, heteroaryloxy,amino, alkylamino, imine, nitrile, acetylide, carboxylate or optionallysubstituted aliphatic, heteroaliphatic, alicyclic, heteroalicyclic,aryl, heteroaryl, alkylaryl or alkylheteroaryl. Two or more of R^(L3)and R^(L4) can be taken together to form a saturated, partiallysaturated or unsaturated 3 to 12 membered, optionally substituted ringsystem, optionally containing one or more heteroatoms, When m′ is 2 ormore, the R^(L3) and R^(L4) on each carbon atom may be the same ordifferent or one or more R^(L3) and R^(L4) on adjacent carbon atoms canbe absent, thereby forming a double or triple bond. It will beappreciated that while the compound has two moieties represented by(—CR^(L3)R^(L4))_(m), both moieties will be identical. In particularlypreferred embodiments, m′ is 1, R^(L4) is H, and R^(L3) is H, hydroxylor a C₁₋₆alkyl, preferably methyl. The stereochemistry of the moietyrepresented by (—CR^(L3)R^(L4))_(m), can either be the same (for exampleRR-lactide or SS-lactide), or different (for example, meso-lactide). Thelactide may be a racemic mixture, or may be an optically pure isomer.Preferably, the lactide has the following formula:

The term “lactone and/or lactide” used herein encompasses a lactone, alactide and a combination of a lactone and a lactide. Preferably, theterm “lactone and/or lactide” means a lactone or a lactide.

Preferred optional substituents of the groups R^(e1), R^(e2), R^(e3),R^(e4), R^(a1), R^(a2), R^(a3), R^(a4), R^(L1), R^(L2), R^(L3) andR^(L4) include halogen, nitro, hydroxyl, unsubstituted aliphatic,unsubstituted heteroaliphatic unsubstituted aryl, unsubstitutedheteroaryl, alkoxy, aryloxy, heteroaryloxy, amino, alkylamino, imine,nitrile, acetylide, and carboxylate.

DETAILED DESCRIPTION

In a first aspect, the present invention provides a method for preparinga block copolymer, using a single catalytic system, wherein the singlecatalytic system comprises a catalyst of formula (I):

Wherein:

[M] is a metal complex having at least one metal atom M coordinated by aligand system;

M is Zn, Cr, Co, Mn, Mg, Fe, Ti, Ca, Ge, Al, Mo, W, Ru, Ni or V;

Z is absent, or is independently selected from -E-, -EX(E)-, or-EX(E)E-,

each E is independently selected from O, S or NR^(Z), wherein R^(Z) isH, or optionally substituted aliphatic, heteroaliphatic, alicyclic,heteroalicyclic, aryl, heteroaryl, alkylaryl or alkylheteroaryl;

X is C or S

R is hydrogen, or optionally substituted aliphatic, heteroaliphatic,alicyclic, heteroalicyclic, aryl, heteroaryl, alkylaryl,alkylheteroaryl, silyl or a polymer; and when Z is absent, R mayadditionally be selected from halide, phosphinate, azide and nitrate;

the method comprising the steps of:

-   -   d) forming a first block by polymerising a first monomer or        combination of monomers selected from the groups (i) to (iii):        -   Group (i): a lactide and/or a lactone,        -   Group (ii): an epoxide and an anhydride, or        -   Group (iii): an epoxide and carbon dioxide,    -   e) optionally contacting the catalyst of formula (I) with a        compound [Y] which is capable converting the group —Z—R, wherein        Z is absent or a group selected from -E-X(E)- or -E-X(E)E-, to a        group —Z—R wherein Z is -E-;    -   f) forming a second block by polymerising a second monomer or        combination of monomers selected from a different group (i)        to (iii) to that selected for the first monomer or combination        of monomers:        -   Group (i): a lactide and/or a lactone,        -   Group (ii): an epoxide and an anhydride, or        -   Group (iii): an epoxide and carbon dioxide,

wherein when the first monomer or combination of monomers is Group (i),Z is -E-; and wherein when the first monomer or combination of monomersis Group (ii) or Group (iii), and the second monomer or combination ofmonomers is Group (i), step b) is performed after step a).

It will be appreciated that the definition of the catalyst system foruse in the method of the present invention is not limiting andencompasses any catalyst of formula (I), in particular any catalyst offormula (I) suitable for polymerisation of an epoxide with carbondioxide, or an anhydride, to form a polycarbonate polyol or polyesterpolyol respectively.

Such known catalyst systems generally comprise a metal, and a ligand.The metal can be selected from Zn, Ni, Ru, Mo, Fe, Mn, Mo, Cr, V, Co,Ti, W, Al, Ca, Ge or Mg. In preferred embodiments, the metal is Zn, Mg,or Co, more preferably Mg or Zn. The catalyst can comprises one or moremetal atoms, such as two metal atoms. The ligand can be a monodentate orpoly dentate ligand, such as a bi-dentate, tri-dentate or tetradentateligand.

In particular, the methods of the present invention can use a metalco-ordination compound comprising the following tetradentate ligands asdisclosed in WO2010/028362, the contents of which are incorporatedherein by reference: salen derivatives; derivatives of salan ligands;bis-2-hydroxybenzamido derivatives; derivatives of the Trost ligand;porphyrin derivatives; derivatives of tetrabenzoporphyrin ligands;derivatives of corrole ligands; phthalocyaninate derivatives; anddibenzotetramethyltetraaza[14]annulene derivatives.

The invention relates to catalysts comprising metal complexes comprisingtwo or metal atoms complexed to one or more multidentate ligand(s) asdisclosed in WO2012/037282, the contents of which are incorporatedherein by reference.

The invention further encompasses the use of catalysts comprising bulkyβ-diiminate (BDI) ligands for example (BDI)-ZnO^(i)Pr as disclosed inCoates et al, J.A.C.S., (2001), 123, 3229-3238, the contents of whichare incorporated herein by reference. An additional example of such acatalyst includes the salen Co(III)X/onium salt catalyst system asdisclosed in Lu et al, J.A.C.S., (2012), 134, 17739-17745, the contentsof which are incorporated herein by reference.

The invention further encompasses, and preferably relates to, catalystscomprising two metal atoms complexed to a multidentate ligand system asdisclosed in WO2009/130470 and WO2013/034750, the entire contents ofwhich are incorporated herein by reference.

Other examples of known catalyst systems for use in the method of thepresent invention include (BDI)Zn—OAc as disclosed in R. C. Jeske, A. M.DiCiccio, G. W. Coates, J. Am. Chem. Soc. 2007, 129, 11330-11331,(salen)Cr—Cl as disclosed in D. J. Darensbourg, R. R. Poland, C.Escobedo, Macromolecules 2012, 45, 2242-2248, (salen)M—Cl, where M isCr, Al, Co or Mn, as disclosed in C. Robert, F. De Montigny, C. M.Thomas, Nature Comm. 2011, 2, 586, (salen)-Co—O₂CPH as disclosed in M.DiCicco, G. W. Coates, J. Am. Soc. 2011, 133, 10724-10727,(Tp-porph)Al—Cl as disclosed in T. Aida, S. Inoue, J. Am. Chem. Soc.1985, 107, 1358-1364 and T. Aida, K. Sanuki, S. Inoue, Macromolecules1985, 18, 1049; (sal*)MCl where M is Al, Cr or Co as disclosed in E.Hosseini Nejad, C. G. W. van Melis, T. J. Vermeer, C. E. Koning, R.Duchateau, Macromolecules, 2012, 45, 1770-1776, (Ph-salen)Cr—Cl asdisclosed in E. Hosseini Nejad, A. Paoniasari, C. E. Koning, R.Duchateau, Polym. Chem, 2012, 3, 1308, the contents of all of which areincorporated herein by reference.

In preferred embodiments of the first aspect, the catalyst of formula(I) is preferably a complex of formula (IA):

wherein

R₁ and R₂ are independently hydrogen, halide, a nitro group, a nitrilegroup, an imine, an amine, an ether group, a silyl ether group, athioether group, a sulfoxide group, a sulfinate group, or an acetylidegroup or an optionally substituted alkyl, alkenyl, alkynyl, haloalkyl,aryl, heteroaryl, alicyclic or heteroalicyclic;

R₃ is optionally substituted alkylene, alkenylene, alkynylene,heteroalkylene, heteroalkenylene, heteroalkynylene, arylene,heteroarylene or cycloalkylene, wherein alkylene, alkenylene,alkynylene, heteroalkylene, heteroalkenylene and heteroalkynylene mayoptionally be interrupted by aryl, heteroaryl, alicyclic orheteroalicyclic;

R₄ is H, or optionally substituted aliphatic, heteroaliphatic,alicyclic, heteroalicyclic, aryl, heteroaryl, alkylheteroaryl oralkylaryl;

R₅ is H, or optionally substituted aliphatic, heteroaliphatic,alicyclic, heteroalicyclic, aryl, heteroaryl, alkylheteroaryl oralkylaryl;

E₁ is C, E₂ is O, S or NH or E₁ is N and E₂ is O;

Z is absent, or is selected from -E-, -EX(E)-, or -EX(E)E-;

X is C or S;

E is —O—, —S—, or NR^(Z), wherein is H, or optionally substitutedaliphatic, heteroaliphatic, alicyclic, heteroalicyclic, aryl,heteroaryl, alkylaryl or alkylheteroaryl;

R is hydrogen, or optionally substituted aliphatic, heteroaliphatic,alicyclic, heteroalicyclic, aryl, heteroaryl, alkylaryl,alkylheteroaryl, silyl or a polymer; and when Z is absent, R mayadditionally be selected from halide, phonsphinate, azide and nitro;

each G is independently absent or a neutral or anionic donor ligandwhich is a Lewis base; and

M is Zn(II), Cr(II), Co(II), Mn(II), Mg(II), Fe(II), Ti(II),Cr(III)-Z—R, Co(III)-Z—R, Mn (III)-Z—R, Fe(III)-Z—R, Ca(II), Ge(II),Al(III)-Z—R, Ti(III)-Z—R, V(III)-Z—R, Ge(IV)-(—Z—R)₂ or Ti(IV)-(—Z—R)₂.

R₁ and R₂ are independently hydrogen, halide, a nitro group, a nitrilegroup, an imine, an amine, an ether group, a silyl ether group, athioether group, a sulfoxide group, a sulfinate group, or an acetylidegroup or optionally substituted alkyl, alkenyl, alkynyl, haloalkyl,aryl, heteroaryl, alicyclic or heteroalicyclic. R₁ and R₂ may be thesame or different. R₁ and R₂ are preferably independently selected fromhydrogen, tBu, Me, CF₃, phenyl, F, Cl, Br, I, NMe₂, NEt₂, NO₂, OMe,OSiEt₃, CNMe, CN or CCPh, more preferably hydrogen, OMe, Me, NO₂,halogen or tBu (e.g. hydrogen or tBu). In certain embodiments, R₂ ishydrogen and R₁ is any one of the groups defined above, preferably NO₂,halogen, tBu, OMe or Me, more preferably tBu, OMe or Me.

R₃ is a disubstituted alkyl, alkenyl, alkynyl, heteroalkyl,heteroalkenyl or heteroalkynyl group which may optionally be interruptedby an aryl, heteroaryl, alicyclic or heterolicyclic group, or may be adisubstituted aryl or cycloalkyl group which acts as a bridging groupbetween two nitrogen centres in the catalyst of formula (IA). Thus,where R₃ is a alkylene group, such as dimethylpropylene, the R₃ grouphas the structure —CH₂—C(CH₃)₂—CH₂—. The definitions of the alkyl, aryl,cycloalkyl etc groups set out above therefore also relate respectivelyto the alkylene, arylene, cycloalkylene etc groups set out for R₃. Incertain embodiments, R₃ is optionally substituted alkylene, alkenylene,alkynylene, heteroalkylene, heteroalkenylene, heteroalkynylene, arylene,heteroarylene or cycloalkylene; wherein alkylene, alkenylene,alkynylene, heteroalkylene, heteroalkenylene and heteroalkynylene mayoptionally be interrupted by aryl, heteroaryl, alicyclic orheteroalicyclic. In particularly preferred embodiments, R₃ is apropylene group which is optionally substituted by aliphatic (preferablyC₁₋₆alkyl) or aryl groups. Preferably R₃ is ethylene,2,2-dimethylpropylene, propylene, butylene, phenylene, cyclohexylene orbiphenylene, more preferably 2,2-dimethylpropylene. When R₃ iscyclohexylene, it can be the racemic, RR— or SS— forms.

R₄ is H, or optionally substituted aliphatic, heteroaliphatic,alicyclic, heteroalicyclic, aryl, heteroaryl, alkylheteroaryl oralkylaryl. Preferably R₄ is independently selected from hydrogen, oroptionally substituted alkyl, alkenyl, alkynyl, aryl or heteroaryl.Exemplary options for R₄ include H, Me, Et, Bn, iPr, tBu or Ph. Morepreferably, R₄ is hydrogen.

R₅ is H, or optionally substituted aliphatic, heteroaliphatic,alicyclic, heteroalicyclic, aryl, heteroaryl, alkylheteroaryl oralkylaryl. Preferably R₅ is independently selected from hydrogen, oroptionally substituted aliphatic or aryl. More preferably, R₅ isselected from hydrogen, alkyl or aryl. Exemplary R₅ groups includehydrogen, methyl, trifluoromethyl, ethyl and phenyl (preferablyhydrogen, trifluoromethyl and methyl). In particularly preferredembodiments, all instances of R₅ are hydrogen.

In certain embodiments, R₁, R₂, R₃, R₄ and R₅ are each independentlyoptionally substituted by halogen, hydroxyl, nitro, carbonate, alkoxy,aryloxy, heteroaryloxy, amino, alkylamino, imine, nitrile, acetylide, orunsubstituted aliphatic, heteroaliphatic, alicyclic, heteroalicyclic,aryl or heteroaryl. Preferably R₁, R₂, R₃, R₄ and R₅ are eachindependently optionally substituted by halogen, hydroxyl, nitro,carbonate, alkoxy, aryloxy, imine, nitrile, acetylide, unsubstitutedaliphatic, unsubstituted alicyclic and unsubstituted aryl.

In certain embodiments, E₁ is C, E₂ is O, S or NH, and preferably E₂ isO. In other embodiments, E₁ is N and E₂ is O. In particularly preferredembodiments, E₁ is C and E₂ is O.

G is either present or absent. When G is not absent, it is a group whichis capable of donating a lone pair of electrons (i.e. a Lewis base). Incertain embodiments, G is a nitrogen containing Lewis base. Each G mayindependently be neutral or negatively charged. If G is negativelycharged, then one or more positive counterions will be required tobalance out the change of the complex. Suitable positive counterionsinclude group 1 metal ions (Na⁺, K⁺, etc), group 2 metal ions (Mg²⁺,Ca²⁺, etc), imidazolium ions, positively charged optionally substitutedheteroaryl, heteroalicyclic or heteroaliphatic groups, ammonium ions(i.e. N(R¹²)₄ ⁺), iminium ions (i.e. (R¹²)₂C═N(R¹²)₂ ⁺, such asbis(triphenylphosphine)iminium ions) or phosphonium ions (P(R¹²)₄ ⁺),wherein each R¹² is independently selected from hydrogen or optionallysubstituted aliphatic, heteroaliphatic, alicyclic, heteroalicyclic, arylor heteroaryl. Exemplary counterions include [H—B]⁺ wherein B isselected from triethylamine, 1,8-diazabicyclo[5.4.0] undec-7-ene and7-methyl-1,5,7-triazabicyclo[4.4.0]dec-5-ene.

G is preferably independently selected from an optionally substitutedheteroaliphatic group, an optionally substituted heteroalicyclic group,an optionally substituted heteroaryl group, a halide, hydroxide,hydride, a carboxylate, an ether, a thioether, carbene, a phosphine, aphosphine oxide, an amine, an acetamide, acetonitrile, an ester, asulfoxide, a sulfonate and water. More preferably, G is independentlyselected from water, an alcohol, a substituted or unsubstitutedheteroaryl (imidazole, methyl imidazole, pyridine,4-dimethylaminopyridine, pyrrole, pyrazole, etc), an ether (dimethylether, diethylether, cyclic ethers, etc), a thioether, carbene, aphosphine, a phosphine oxide, a substituted or unsubstitutedheteroalicyclic (morpholine, piperidine, tetrahydrofuran,tetrahydrothiophene, etc), an amine, an alkyl amine (trimethylamine,triethylamine, etc), acetonitrile, an ester (ethyl acetate, etc), anacetamide (dimethylacetamide, etc), a sulfoxide (dimethylsulfoxide,etc), a carboxylate, a hydroxide, hydride, a halide, a nitrate, asulfonate, etc. In some embodiments, one or both instances of G isindependently selected from optionally substituted heteroaryl,optionally substituted heteroaliphatic, optionally substitutedheteroalicyclic, halide, hydroxide, hydride, an ether, a thioether,carbene, a phosphine, a phosphine oxide, an amine, an alkyl amine,acetonitrile, an ester, an acetamide, a sulfoxide, a carboxylate, anitrate or a sulfonate. In certain embodiments, G may be a halide;hydroxide; hydride; water; a heteroaryl, heteroalicyclic or carboxylategroup which are optionally substituted by alkyl, alkenyl, alkynyl,alkoxy, halogen, hydroxyl, nitro or nitrile. In preferred embodiments, Gis independently selected from halide; water; a heteroaryl optionallysubstituted by alkyl (e.g. methyl, ethyl etc), alkenyl, alkynyl, alkoxy(preferably methoxy), halogen, hydroxyl, nitro or nitrile. In someembodiments, one or both instances of G is negatively charged (forexample, halide). In further embodiments, one or both instances of G isan optionally substituted heteroaryl. Exemplary G groups includechloride, bromide, pyridine, methylimidazole (for example N-methylimidazole) and dimethylaminopyridine (for example,4-methylaminopyridine).

Preferably G is absent.

It will be appreciated that when a G group is present, the G group maybe associated with a single M metal centre as shown in formula (IA), orthe G group may be associated with both metal centres and form a bridgebetween the two metal centres.

Preferably M is Zn(II), Cr(III), Cr(II), Co(III), Co(II), Mn(III),Mn(II), Mg(II), Fe(II), Fe(III), Ca(II), Ge(II), Ti(II), Al(III),Ti(III), V(III), Ge(IV) or Ti(IV), more preferably Zn(II), Cr(III),Co(II), Mn(II), Mg(II), Fe(II) or Fe(III), and most preferably Zn(II) orMg(II). It will be appreciated that when M is Cr(III), Co(III), Mn(III)or Fe(III), the catalyst of formula (IA) will contain an additional —Z—Rgroup co-ordinated to the metal centre, wherein —R—R is as definedherein. It will also be appreciated that when M is Ge(IV) or Ti(IV), thecatalyst of formula (IA) will contain two additional —Z—R groupsco-ordinated to the metal centre, wherein —Z—R is as defined above. Incertain embodiments, when M is Ge(IV) or Ti(IV), both G may be absent.

The skilled person will also appreciate that each M may be the same (forexample, both M may be Mg, Zn, Fe or Co) or each M may be different andcan be present in any combination (for example, Fe and Zn, Co and Zn, Mgand Fe, Co and Fe, Mg and Co, Cr and Mg, Cr and Zn, Mn and Mg, Mn andZn, Mn and Fe, Cr and Fe, Cr and Co, Al and Mg, Al and Zn etc). When Mis the same metal, it will be appreciated that each M may be in the sameoxidation state (for example both M may be Co(II), Fe(II) or Fe(III)),or in a different oxidation state (for example, one M may be Co(II) andthe other M may be Co(III), one M may be Fe(II) and the other M may beFe(III), or one M may be Cr(II) and the other M may be Cr(III)).

—Z— is either absent or selected from -E-, -E-X(E)- or -E-X(E)-E-.

X is C or S, preferably C.

E is O, S, or NR^(Z).

When Z is -E-X(E)-, -E-X(E)- is preferably —O—(CO)—, —NR^(Z)—CO)—,—O—C(═NR^(Z))—, —O—C(S)—, —O—S(O)—, —NR^(Z)—S(O)— or —O—S(═NR^(Z))—.

When Z is -E-X(E)-E-, -E-X(E)-E-. is preferably —O—(CO)—O,—NR^(Z)—C(O)—O—, —NR^(Z)—C(O)—NR^(Z), —O—C(═NR^(Z))—O—,—O—C(═NR^(Z))—NR^(Z)—, —O—C(S)—O—, —O—C(O)—NR^(Z), —O—S(O)—O—,—NR^(Z)—S(O)—O—, —O—S(O)—NR^(Z).

Preferably, each occurrence of E is O.

In certain embodiments, each E is O and X is C.

Each NR^(Z) is independently H, or optionally substituted aliphatic,heteroaliphatic, alicyclic, heteroalicyclic, aryl, heteroaryl, alkylarylor alkylheteroaryl. Preferably NR^(Z) is hydrogen or C₁₋₆alkyl.

R is hydrogen, or optionally substituted aliphatic, heteroaliphatic,alicyclic, heteroalicyclic, aryl, heteroaryl, alkylaryl, alkylheteroarylor silyl. Preferably, R is an optionally substituted alkyl, alkenyl,alkynyl, aryl, alkylaryl, cycloalkyl, cycloalkenyl, cycloalkynyl,heteroaryl, cycloheteroalkyl, alkylheteroaryl or silyl. More preferably,R is C₁₋₁₂alkyl, cycloalkyl or aryl (for example, methyl, ethyl,n-propyl, isopropyl, n-butyl, tert-butyl, phenyl, cyclohexyl etc).

When —Z— is absent, in addition to the above groups, R may also be ahalide, phosphinate, azide or nitrate.

Preferably, R may be substituted by halogen, hydroxyl, nitro,unsubstituted aryl, unsubstituted alkyl, unsubstituted alkenyl,unsubstituted alkoxy and unsubstituted aryloxy. For example, R may be analkyl group substituted by halogen, for instance R may be CF₃.

It will also be appreciated that R can be a polymer chain. For example,R may be a polycarbonate or a polyester.

The catalyst of formula (IA) has two or more occurrences of —Z—R,depending on the oxidation state of the metal M. Each —Z—R may be thesame, or different.

The skilled person will also understand that the moiety in the group —Rwhich is attached to the group —Z— will not be a heteroatom (forexample, O, S or N) or a group C═E′, where E′ is a heteroatom (forexample O, S, or N).

In particularly preferred embodiments, R₁ and R₂ are independentlyhydrogen, or optionally substituted alkyl, alkenyl, halogen, hydroxyl,nitro, alkoxy, aryl, heteroaryl, alkylaryl and alkylheteroaryl; R₃ isoptionally substituted alkylene or arylene; R₄ is hydrogen, oroptionally substituted alkyl or heteroaryl; R₅ is hydrogen or optionallysubstituted alkyl; E₁ is C and E₂ is O; M is Mg, Zn, Fe or Co; Z iseither absent or selected from —O—R, O—C(O)—R or —OC(O)—O—R; R isoptionally substituted alkyl, alkenyl, cycloalkyl, aryl, heteroaryl,alkylaryl or alkylheteroaryl; or when Z is absent, R is phosphinate orhalide; G is either absent, or is selected from optionally substitutedheteroaryl or halide. It will be appreciated that when G is a halogen, acounterion must be present. Preferably, the counterion is [H—B]⁺,wherein B is preferably selected from NEt₃,1,8-diazabicyclo[5.4.0]undec-7-ene (DBU) and7-methyl-1,5,7-triazabicyclo[4.4.0]dec-5-ene (MTBD).

Exemplary catalysts of formula (IA) are as follows:

[L¹Mg₂Cl₂(methylimidazole)],

[L₁Mg₂Cl₂(dimethylaminopyridine)],

[L₁Mg₂Br₂(dimethylaminopyridine)],

[L¹Zn₂(F₃CCOO)₂],

[L¹Zn₂(OOCC(CH₃)₃)₂],

[L¹Zn₂(OC₆H₅)₂],

[L¹Fe₂Cl₄],

[L¹Co₂(OAc)₃],

[L¹Zn₂(adamantyl carbonate)₂],

[L¹Zn₂(pentafluorobenzoate)₂],

[L¹Zn₂(diphenylphosphinate)₂],

[L¹Zn₂(bis(4-methoxy)phenyl phosphinate)₂],

[L¹Zn₂(hexanoate)₂],

[L¹Zn₂(octanoate)₂],

[L¹Zn₂(dodecanoate)₂],

[L¹Mg₂(F₃CCOO)₂],

[L¹Mg₂Br₂],

[L¹Zn₂(C₆F₅)₂],

[L¹Zn₂(C₆H₅)₂] and

[L¹Zn₂(OiPr)₂].

The compound [Y] which can be used in the first aspect of the presentinvention must be capable of converting the group —Z—R, wherein Z isabsent or a group selected from -E-C(E)- or -E-C(E)E-, to a group —Z—Rwherein Z is -E-. In other words, the compound [Y] must be capable ofinserting into the bond between the metal atom in the metal complex [M]and the group —Z—R in order to switch the ligand attached to the metalatom from —R, -E-C(E)-R or E-C(E)-E-R to -E-R.

The compound [Y] may be a compound having a three, four or five memberedsaturated ring and at least one heteroatom selected from O, S or N. Inpreferred embodiments, the compound [Y] may be an epoxide, an aziridine,an episulfide, an oxetane, a thietane, an azetidine, a saturated furan,a saturated thiophene or a pyrrolidine.

In certain embodiments, the compound [Y] has the following formula:

Wherein

A is O, S or NR^(A); (preferably A is O)

j is 1, 2, or 3;

R^(A) is hydrogen, halogen, hydroxyl, alkoxy, aryloxy, heteroaryloxy, oraliphatic, heteroaliphatic, alicyclic, heteroalicyclic, aryl,heteroaryl, alkylaryl or alkylheteroaryl;

Each R^(A1), R^(A2), R^(A3) and R^(A4) is independently selectedhydrogen, halogen, hydroxyl, nitro, alkoxy, aryloxy, heteroaryloxy,amino, alkylamino, imine, nitrile, acetylide, carboxylate or optionallysubstituted aliphatic, heteroaliphatic, alicyclic, heteroalicyclic,aryl, heteroaryl, alkylaryl or alkylheteroaryl; or two or more ofR^(A1), R^(A2), R^(A3) and R^(A4) can be taken together to form asaturated, partially saturated or unsaturated 3 to 12 membered,optionally substituted ring system, optionally containing one or moreheteroatoms. For example, each R^(A1), R^(A2), R^(A3) and R^(A4) may beH; R^(A1), R^(A2) and R^(A3) may be H and one or more R^(A4) may be arylor aliphatic, preferably phenyl or alkyl; R^(A1) and R^(A4) may be H,and R^(A2) and R^(A3) may be taken together to form a six to 10 memberedcarbon ring (saturated, unsaturated or partially saturated. For example,the compound [Y] may be:

Preferred optional substituents of the groups R^(A1), R^(A2), R^(A3) andR^(A4) include halogen, nitro, hydroxyl, unsubstituted aliphatic,unsubstituted heteroaliphatic unsubstituted aryl, unsubstitutedheteroaryl, alkoxy, aryloxy, heteroaryloxy, amino, alkylamino, imine,nitrile, acetylide, and carboxylate.

In preferred embodiments, the compound [Y] is an epoxide. When thecompound [Y] is an epoxide, it will be appreciated that it may be thesame, or different, to the epoxide monomer to be polymerised. In highlypreferred embodiments, the compound [Y] is an epoxide which is the sameas the epoxide to be polymerised by the method of the first aspect.

The polymerisation of an epoxide and carbon dioxide has been performedin the presence of various catalysts of formula (I), for example, thecatalysts described in WO2009/130470 and WO 2013/034750 (each of whichare herein incorporated by reference in their entirety). The reactionbetween the monomers, carbon dioxide and the epoxide, at the metal atomM proceeds by the following pathway in which the carbon dioxide insertsinto the bond between the metal atom and the labile ligand -E-R(represented below by —O—R) to form a carbonate group attached to themetal atom, followed by the insertion of an epoxide between thecarbonate group and the metal atom, in order to regenerate the group—O—R:

The skilled person will understand that R^(P) represents the growingpolymer chain and will therefore increase in size after each addition ofCO₂/epoxide monomer.

The polycarbonates produced by the reaction between an epoxide andcarbon dioxide in the presence of a catalyst of formula (I) may berepresented as follows:

Wherein n₁ is 1 to 1,000,000, for example 10 to 100,000, such as 100 to10,000, e.g. 10 to 1,000.

It will be understood that the moiety attached to the metal atom M willeither be -E-R or -E-X(E)-R (i.e. E is O and R is R^(P)). As thecopolymerisation of carbon dioxide and an epoxide is generally carriedout using a vast excess of carbon dioxide (due to the low cost andavailability of this reagent, and to ensure entire consumption of theepoxide monomer), the moiety attached to the metal complex [M] willpredominantly be —O—C(O)—O—R once the reaction has terminated.

It has been surprisingly found that the catalysts as described in WO2009/130470 and WO 2013/034750 are also capable of polymerising anepoxide and an anhydride. This reaction is as set out in the fourthaspect of the application below, with the catalysts defined as catalystsof formula (IA).

The reaction between the anhydride and the epoxide monomers at the metalcomplex [M] proceeds by the following pathway in which the anhydrideinserts into the bond between the metal atom and the labile ligand -E-R(represented below by —O—R^(P)) to form an ester group attached to themetal atom, followed by the insertion of an epoxide between the estergroup and the metal atom, in order to regenerate the group —O—R^(P):

R^(P) represents the growing polymer chain, and therefore increases insize upon the addition of each epoxide/anhydride monomer.

The polyesters produced by the reaction between an epoxide and ananhydride in the presence of a catalyst of formula (I) may berepresented as follows:

Wherein n₂ is 1 to 1,000,000, for example 10 to 100,000, such as 100 to10,000, e.g. 10 to 1,000.

The inventors have found that, in the copolymerisation of an epoxide andan anhydride, the moiety attached to the metal complex [M] will eitherbe —O—C(O)—R or —O—R. When the reaction terminates, the moiety attachedto the metal complex will depend on which of the monomers is in excess.

The present invention further provides the use of catalysts of formula(IA) for initiating the ring opening of lactide and/or lactone monomers.When used in this manner, it is required that the labile ligand is —Z—Ris —O—R, S—R or —NR^(Z)—R.

The ring opening of a lactide and a lactone in the presence of acatalyst system having a catalyst of formula (I) may be represented asfollows:

In the above schemes, n₃ and n₄ are independently selected from 1 to10,000, for example, 1 to 5000, such as 10 to 1000.

The inventive methods described herein can therefore be used to ringopen a lactide and/or a lactone in order to make dimers, trimers,tetramers, penatmers etc (i.e. when n³ or n⁴=2, 3, 4, 5) or polymers(i.e. when n³ or n⁴=1 to 10,000). This method is described in the thirdaspect of the present invention.

The complexes of formula (I), in particular compounds of formula (IA),retain their active centres after the initial polymerisation hasproceeded to completion. In other words, the metal complex [M] at theend of the polymer chain is a “dormant” catalytic species once one ormore of the initial monomer species has been used up. This means thatpropagation may resume upon the introduction of additional monomer(s).

In a particular embodiment of the first aspect of the invention, thereis provided a method for producing a polycarbonate-polyester blockcopolymer, the method comprising initially polymerising carbon dioxideand an epoxide in the presence of a single catalytic system having acatalyst of formula (I) to form a polycarbonate block and, addinganhydride (and optionally further epoxide, which may be the same ordifferent to the epoxide used to produce the first block) to thereaction mixture. This reaction may be represented as follows:

In an alternative embodiment, there is provided a method for producing apolyester-polycarbonate block copolymer, the method comprising initiallypolymerising an epoxide and an anhydride epoxide in the presence of asingle catalytic system having a catalyst of formula (I) to form apolyester block, and subsequently adding carbon dioxide (and optionallyfurther epoxide, which may be the same or different to the epoxide usedto produce the first block) to the reaction mixture. This reaction maybe represented as follows:

In both of the above reactions, it will be appreciated that furtherepoxide will need to be added to the reaction mixture in order toproduce the second block if all of the epoxide has been consumed in theproduction of the first block.

As discussed above, the moiety attached to the metal complex [M] afterthe copolymerisation of an anhydride or carbon dioxide with an epoxidehas taken place will be an ester group (—OC(O)—R) or a carbonate group(—OC(O)—O—R), respectively, if the reaction is carried out with anexcess of carbon dioxide/anhydride.

The inventors have recognised that, in order to use lactides and/orlactones in the method of the first aspect, it is necessary tospecifically tailor the group attached to the metal complex [M] so thatring opening polymerisation can proceed.

The inventors have found that it is possible to “convert” the moietyattached to the metal complex [M] by adding a compound [Y] to the singlecatalytic system comprising a catalyst of formula (I). The compound [Y]is capable converting the group —Z—R, wherein Z is absent or a groupselected from -E-X(E)- or -E-X(E)E- (for example, —O—C(O)—R or—O—C(O)—O—R), to a group -E-R (for example, —O—R). The compound [Y]inserts in between the metal complex [M] and the group —R, -E-X(E)-R or-E-X(E)-E-R, thereby ensuring that the moiety attached to the metalcomplex [M] is -E-R.

In an alternative embodiment of the first aspect, there is provided amethod for producing a polyester-polyester, or a polycarbonate-polyesterblock copolymer, the method comprising initially polymerising an epoxideand an anhydride, or an epoxide and carbon dioxide, using a singlecatalyst system having a catalyst of formula (I) to form a firstpolyester block or a polycarbonate block, respectively, converting themoiety attached to the metal complex [M] at the end of the polymer chainfrom an ester group (—OC(O)—) or a carbonate group (—OC(O)—O—), to agroup -E- (for example an alkoxy group, and alkylthio group or a primaryor secondary amine group) using a compound [Y], and then adding alactide and/or a lactone. These reactions maybe represented as follows:

The skilled person will appreciate that the compound [Y] may be addedafter the first block has been prepared. Alternatively, it will beappreciated that if all of the epoxide is not consumed in the formationof the first block, the remaining epoxide monomer will insert into thebond between the complex [M] and the ester group —OC(O)—R or thecarbonate group —O—C(O)O—R, thereby functioning as the compound [Y].Therefore, the compound [Y] may be present in the initial reactionmixture, for example, in the form of an excess of epoxide.

The lactide and/or lactone may be added at the same time as, or after,the addition of compound [Y] to the single catalytic system.

In an alternative embodiment of the first aspect, there is provided amethod for producing a polyester-polyester, or polyester-polycarbonateblock copolymer, the method comprising ring opening a lactide and/or alactone, and subsequently adding an epoxide and carbon dioxide or anepoxide and an anhydride. It will be appreciated that if the first blockis prepared by ring opening of a lactide and/or a lactone, the catalystsystem must contain a catalyst of formula (I), where the labile ligand—Z—R is -E-R.

It is possible that the epoxide monomer used to produce the second blockmay be added to the single catalytic system at the same time as theanhydride/carbon dioxide, or it may be present in the single catalyticsystem prior to the production of the first block.

This reaction can be represented as follows:

It will be appreciated that when the first block is prepared by ringopening a lactide and/or a lactone, a compound [Y] can be used totransform catalysts of formula (I) where —Z—R is not -E-R into catalystswhere —Z—R is -E-R.

Alternatively, catalysts of formula (I) where —Z—R is —R (i.e. wherein Eis absent) can be transformed into catalysts formula (I) where —Z—R is-E-R by contacting the catalyst of formula (I) with compound containingan alcohol, a thiol or a primary or secondary amine. For example, thecompound may an aliphatic, heteroaliphatic, aryl, heteroaryl, alicyclicor heteroalicyclic group which is substituted by one or more (e.g. twoor more) —OH, —SH, or —NHR^(Z) groups. For instance, the compound may beisopropyl alcohol, 1, 2-cyclohenanediol, 1,2-ethylene glycol,1,2-propylene glycol, 1,3-propylene glycol, benzyl alcohol, ethanol,methanol, n-propanol, a hexose, a pentose, poly(ethyleneglycol), etc.Thus, it is possible to produce the desired catalyst for step a) of thefirst aspect in situ.

In certain embodiments, the method of the first aspect further comprisesthe step of forming a third block by polymerising a third monomer orcombination of monomers selected from the groups:

-   -   Group (I): a lactide and/or a lactone;    -   Group (ii): an epoxide and an anhydride; and    -   Group (iii): an epoxide and carbon dioxide.

If Group (i) is added to the single catalytic system, the method mayalso comprise the step of contacting the single catalytic system with acompound [Y]. This may be done prior to, or at the same time as,contacting the single catalytic system with the third monomer orcombination of monomers.

In certain embodiments, the third monomer or combination of monomers isdifferent from the Group of monomer used to produce the first and secondblocks. In other embodiments, the third monomer or combination ofmonomers is selected from the same group of monomer or combination ofmonomers used to produce the first block.

The tri-block copolymer produced may be an ABC block copolymer, i.e.each of the blocks is different. Alternatively, the tri-block copolymermay be an ABA block copolymer, i.e. when the first and the third blocksare the same.

The skilled person will also appreciate that the method according to thefirst aspect can also be used to produce block copolymers having four,five, six, seven, etc blocks, and that the order and identity of theblocks can be tailored accordingly. For example, the method of the firstaspect may be used to produce block copolymers having alternatingblocks, such as ABABA, or ABCABC. Alternatively, each of the blocks maybe different.

It will be appreciated that for each of the various embodimentsdescribed for the first aspect, the single catalytic system may compriseany compound according to formula (I), and preferably comprises acompound of formula (IA).

In a second aspect, the present invention provides a method forproducing a block copolymer, said block copolymer having a first andsecond block, using a single catalytic system, wherein the singlecatalytic system comprises a catalyst of formula (I):

Wherein:

[M] is a metal complex having at least one metal atom M coordinated by aligand system;

M is Zn, Cr, Co, Mn, Mg, Fe, Ti, Ca, Ge, Al, Mo, W, Ru, Ni or V;

Z is absent, or is independently selected from -E-, -EX(E)-, or-EX(E)E-,

each E is independently selected from O, S or NR^(Z), wherein R^(Z) isH, or optionally substituted aliphatic, heteroaliphatic, alicyclic,heteroalicyclic, aryl, heteroaryl, alkylaryl or alkylheteroaryl;

X is C or S

R is hydrogen, or optionally substituted aliphatic, heteroaliphatic,alicyclic, heteroalicyclic, aryl, heteroaryl, alkylaryl,alkylheteroaryl, silyl or a polymer; and when Z is absent, R may also beselected from halide, phosphinate, azide and nitrate;

the method comprising the steps of:

-   -   c) providing a mixture comprising:        -   I. an epoxide;        -   II. a first monomer or combination of monomers selected from            a group (i) to (iii):            -   Monomer (i): a lactide and/or a lactone,            -   Monomer (ii): an anhydride, or            -   Monomer (iii): carbon dioxide, and        -   III. a second monomer or combination of monomers selected            from a different group (i) to (iii) to that selected for the            first monomer or combination of monomers:            -   Monomer (i): a lactide and/or a lactone,            -   Monomer (ii): an anhydride, or            -   Monomer (iii): carbon dioxide; and    -   d) contacting the mixture with the single catalytic system;

wherein the rate of insertion of the first monomer or combination ofmonomers into the bond between the metal complex [M] and the ligand —Z—Ris faster than the rate of insertion of the second monomer orcombination of monomers into the bond between the metal complex [M] andthe ligand —Z—R.

When the first monomer or combination of monomers is Group (i), either—Z—R is -E-R, or the mixture comprises a compound [Y].

When the second monomer or combination of monomers is Group (i), themixture comprises a compound [Y].

By “one-pot”, it is meant that the block copolymers are formed in situ,in the presence of the single catalytic system, without any sequentialaddition of monomer. In other words, all of the monomers are added tothe reaction mixture, with the single catalyst system comprising acatalyst of formula (I), at the start of the reaction. The reaction willthen selectively form block copolymers from the pool of monomersavailable, with exquisite selectivity.

The catalyst system can comprise a catalyst of formula (IA) as definedin the first aspect. The compound [Y] is as defined in the first aspect.

The inventors have discovered that nature of the polymer block formedwill depend on the moiety at the end of the growing polymer chainattached to the metal complex [M], as well as the relative rates (r) atwhich each of the monomers insert into the bond between the metalcomplex and the ligand —Z—R. r depends on the rate constant of themonomer and the concentration of each of the components in the reactionmixture. The relative rates of insertion of the monomers can bedetermined by exposing one or more of the monomers to a catalyst offormula (I), and monitoring the rate at which the monomer(s) isconsumed, or the rate at which polymer is produced. This can be done,for example, using quantitative spectroscopic or analytic techniqueswhich are well known in the art, such as attenuated total reflectance IRspectroscopy (ATRIR), NMR, optical absorption spectroscopy, IR, ortitration.

For example, when —Z—R is a group which is capable of polymerising alactide and/or a lactone, an epoxide and carbon dioxide, and an epoxideand an anhydride (i.e. -E-R, in particular —O—R) the different rates ofinsertion may be represented as follows:

It will be appreciated that R^(P) represents the growing polymer chain,and its' structure will depend on the identity of the monomers beingpolymerised. It will be understood that the relative rates of insertionwill affect the order in which the blocks are produced.

In certain instances, r_(anh) may be faster than r_(CO2). Alternatively,r_(CO2) may be faster than r_(anh). In certain instances, r_(lac1/lac2)is slower than both r_(anh) and r_(CO2), and faster than r_(epox′) andr_(epox″). However, r_(lac1/lac2) may be faster than r_(anh), r_(CO2),r_(epox′) and r_(epox′). For the catalysts of the present invention,r_(epox′) will be the same as, or similar to, r_(epox″), and both willbe slower than r_(lac1/lac2), r_(anh) and r_(CO2).

In certain embodiments, for example, when the catalyst of formula (I) isa catalyst of formula (IA) as defined in the first aspect of theinvention, r_(anh)>r_(CO2)>r_(lac1/lac2)>r_(epox′)≈r_(epox″).

In such embodiments of the second aspect, the first monomer orcombination of monomers is an anhydride, and the second monomer orcombination of monomers is carbon dioxide. In this case, the singlecatalyst system will initially selectively form a polyester block (afirst block) by polymerising the epoxide and the anhydride. Once theanhydride has been consumed, the metal complex [M] at the end of thepolyester chains can polymerise the carbon dioxide with any remainingepoxide to form a polycarbonate block (a second block). For a polyesterblock and a polycarbonate block to form, it is preferable for theinitial reaction mixture to comprise a greater number of molarequivalents of epoxide than the number of molar equivalents ofanhydride. In preferred embodiments, the number of molar equivalents ofepoxide is 1, 2, 3, 4, 5, 6, 7, 8, 9 or 10 times greater than the numberof molar equivalents of anhydride.

In an alternative of such embodiment, the first monomer or combinationof monomers is an anhydride, and the second monomer or combination ofmonomers is a lactide and/or a lactone, in which case, the catalystsystem will initially selectively form a polyester block (a first block)by polymerising the epoxide and the anhydride. The ring openingpolymerisation will proceed to form a second block once the anhydridemonomer has been consumed, and the moiety attached to the metal complex[M] has been converted from an ester (—OC(O)—R) to a group -E-R(preferably —O—R), by using a compound [Y]. The second block will alsobe a polyester, which is different to the first polyester block. For theabove di-block polyester to form, it is preferable for the number ofmolar equivalents of epoxide, plus the number of molar equivalents ofthe compound [Y] to be greater than the number of molar equivalents ofanhydride. The compound [Y] is preferably an epoxide (which ispreferably the same as the epoxide monomer used in the formation of thefirst block).

In a further alternative of such embodiment, the first monomer orcombination of monomers is carbon dioxide and the second monomer orcombination of monomers is a lactide and/or a lactone. In this instance,the catalyst system will initially selectively form a polycarbonateblock (a first block) by polymerising the epoxide and the carbondioxide. The ring opening polymerisation can proceed (thereby formingthe second block, which is a polyester) once the carbon dioxide monomerhas been consumed (or removed, for example, by the application of avacuum), and the moiety attached to the metal complex [M] has beenconverted from a carbonate (—OC(O)O—R) to a group -E-R (preferably—O—R), by using a compound [Y]. Preferably, the number of molarequivalents of epoxide, plus the number of molar equivalents of thecompound [Y] is greater than the number of molar equivalents of carbondioxide. The compound [Y] is preferably an epoxide (which is preferablythe same as the epoxide monomer used in the formation of the firstblock).

In a further alternative embodiment, the first monomer or combination ofmonomers is carbon dioxide and the second monomer or combination ofmonomers is an anhydride, in which case, the single catalytic systemwill initially selectively form a polycarbonate block first, beforeforming the polyester block (the second block). The initial reactionmixture preferably comprises a greater number of molar equivalents ofepoxide than the number of molar equivalents of carbon dioxide.

In a further alternative embodiment, the first monomer or combination ofmonomers is a lactide and/or a lactone and the second monomer orcombination of monomers is carbon dioxide or an anhydride. In this case,the single catalytic system will initially selectively form a firstpolyester block by ring opening the lactide and/or lactone. Once thelactide and/or lactone has been consumed, the single catalytic systemcan polymerise the epoxide and the carbon dioxide or anhydride in orderto form a second block which is a polycarbonate or a polyester (which isdifferent to the first block), respectively.

In a further embodiment of the second aspect, the reaction mixturecomprises a third monomer or combination of monomers selected from agroup which is different from the first and second monomers orcombination of monomers:

-   -   Monomer (i): a lactide and/or a lactone,    -   Monomer (ii): an anhydride, or    -   Monomer (iii): carbon dioxide.

Where the rate of insertion of the first and second monomers are aspreviously described, and where the rate of insertion of the thirdmonomer or combination of monomers into the bond between the metalcomplex [M] and the ligand —Z—R is slower than both the rate ofinsertion of the first monomer or combination of monomers into the bondbetween the metal complex [M] and the ligand —Z—R, and the rate ofinsertion of the second monomer or combination of monomers into the bondbetween the metal complex [M] and the ligand —Z—R.

When the third monomer or combination of monomers is Monomer (i), thereaction mixture will comprise a compound [Y].

In certain embodiments, when the first monomer or combination ofmonomers is an anhydride, the second monomer or combination of monomersis carbon dioxide and the third monomer or combination of monomers is alactide and/or a lactone, the single catalytic system will initiallyselectively form a first block (which is a polyester) from the pool ofmonomers by polymerising the anhydride and the epoxide. Once theanhydride has been consumed, the catalytic system can selectivelypolymerise the remaining epoxide and the carbon dioxide, thereby forminga second block, which is a polycarbonate. The ring opening of thelactide and/or lactone can proceed to form a third block once the carbondioxide monomer has been consumed (or removed, for example by theapplication of a vacuum), and the moiety attached to the metal complex[M] has been converted from a carbonate (—OC(O)O—R) to a group -E-R(preferably —O—R), by using a compound [Y]. It will be appreciated thatthe third block will be a polyester, which is different to the firstblock. The number of molar equivalents of epoxide, plus the number ofmolar equivalents of the compound [Y] is preferably greater than thenumber of molar equivalents of anhydride, plus the number of molarequivalents of carbon dioxide. The compound [Y] is preferably an epoxide(which is preferably the same as the epoxide monomer used in theformation of the first and second blocks).

In an alternative embodiment, the first monomer or combination ofmonomers is carbon dioxide, the second monomer or combination ofmonomers is an anhydride and the third monomer or combination ofmonomers is a lactide and/or a lactone, in which case the singlecatalytic system will initially selectively form a first block (which isa polycarbonate) from the pool of monomers by polymerising the carbondioxide and the epoxide. Once the carbon dioxide has been consumed (orremoved, for example by application of a vacuum), the catalytic systemcan selectively polymerise the remaining epoxide and the anhydride,thereby forming a second block, which is a polyester. The ring openingof the lactide and/or lactone will then proceed to form a third blockafter the anhydride monomer has been consumed, and the moiety attachedto the metal complex [M] has been converted from a carbonate (—OC(O)O—R)to a group -E-R (preferably —O—R), by using a compound [Y]. Preferably,the number of molar equivalents of epoxide, plus the number of molarequivalents of the compound [Y] is preferably greater than the number ofmolar equivalents of anhydride, plus the number of molar equivalents ofcarbon dioxide. The compound [Y] is preferably an epoxide (which ispreferably the same as the epoxide monomer used in the formation of thefirst and second blocks).

In a further alternative embodiment, first monomer or combination ofmonomers is a lactide and/or a lactone, the second monomer orcombination of monomers is carbon dioxide and the third monomer orcombination of monomers is an anhydride, in which case the singlecatalytic system will initially ring open the lactide and/or lactone inorder to form a polyester block (a first block). Once the lactide and/orlactone has been consumer, the single catalytic system can polymerisethe epoxide and the carbon dioxide, thereby forming a polycarbonateblock (a second block). After the carbon dioxide has been consumed (orremoved, for example by application of a vacuum), the catalytic systemcan selectively polymerise the remaining epoxide and the anhydride,thereby forming a third block, which is a polyester that is differentfrom the first block. Preferably, the number of molar equivalents ofepoxide is greater than the number of molar equivalents of carbondioxide.

In a further alternative embodiment, first monomer or combination ofmonomers is a lactide and/or a lactone, the second monomer orcombination of monomers is an anhydride and the third monomer orcombination of monomers is carbon dioxide, in which case the singlecatalytic system will initially ring open the lactide and/or lactone inorder to form a polyester block (a first block). Once the lactide and/orlactone has been consumed, the single catalytic system can polymerisethe epoxide and the anhydride, thereby forming a second block which is apolyester that is different from the first block. Once the anhydride hasbeen consumed, the catalytic system can selectively polymerise theremaining epoxide and the carbon dioxide, thereby forming a third block,which is a polycarbonate.

In particularly preferred embodiments:

-   -   the first monomer or combination of monomers is anhydride and        the second monomer or combination of monomers is carbon dioxide;    -   the first monomer or combination of monomers is an anhydride and        the second monomer or combination of monomers is a lactide        and/or lactone;    -   the first monomer or combination of monomers is carbon dioxide        and the second monomer or combination of monomers is a lactide        and/or lactone; and    -   the first monomer or combination of monomers is anhydride, the        second monomer or combination of monomers is carbon dioxide, and        the third monomer or combination of monomers is a lactide and/or        lactone.

In each of the above embodiments of the second aspect, the anhydride ispreferably phthalic anhydride, the epoxide is preferablycyclohexeneoxide, the lactide and/or lactone is preferably caprolactoneand the compound [Y] is preferably cyclohexeneoxide. Furthermore, thesingle catalytic system preferably comprises a catalyst of formula (IA),more preferably, [L¹Zn₂(OAc)₂] or [L¹Zn₂(OiPr)₂].

In a third aspect of the invention, there is provided a method forproducing a polyester, comprising contacting a lactone and/or a lactidewith a catalyst system having a catalyst of formula (IA):

wherein

R₁ and R₂ are independently hydrogen, halide, a nitro group, a nitrilegroup, an imine, an amine, an ether group, a silyl ether group, athioether group, a sulfoxide group, a sulfinate group, or an acetylidegroup or an optionally substituted alkyl, alkenyl, alkynyl, haloalkyl,aryl, heteroaryl, alicyclic or heteroalicyclic;

R₃ is optionally substituted alkylene, alkenylene, alkynylene,heteroalkylene, heteroalkenylene, heteroalkynylene, arylene,heteroarylene or cycloalkylene, wherein alkylene, alkenylene,alkynylene, heteroalkylene, heteroalkenylene and heteroalkynylene mayoptionally be interrupted by aryl, heteroaryl, alicyclic orheteroalicyclic;

R₄ is H, or optionally substituted aliphatic, heteroaliphatic,alicyclic, heteroalicyclic, aryl, heteroaryl, alkylheteroaryl oralkylaryl;

R₅ is H, or optionally substituted aliphatic, heteroaliphatic,alicyclic, heteroalicyclic, aryl, heteroaryl, alkylheteroaryl oralkylaryl;

E₁ is C, E₂ is O, S or NH or E₁ is N and E₂ is O;

R is hydrogen, or optionally substituted aliphatic, heteroaliphatic,alicyclic, heteroalicyclic, aryl, heteroaryl, alkylaryl, alkylheteroarylsilyl, or a polymer;

Z is -E-;

E is —O—, —S—, or NR^(Z), wherein is H, or optionally substitutedaliphatic, heteroaliphatic, alicyclic, heteroalicyclic, aryl,heteroaryl, alkylaryl or alkylheteroaryl;

each G is independently absent or a neutral or anionic donor ligandwhich is a Lewis base; and

M is Zn(II), Cr(II), Co(II), Mn(II), Mg(II), Fe(II), Ti(II),Cr(III)-Z—R, Co(III)-Z—R, Mn (III)-Z—R, Fe(III)-Z—R, Ca(II), Ge(II),Al(III)-Z—R, Ti(III)-Z—R, V(III)-Z—R, Ge(IV)-(—Z—R)₂ or Ti(IV)-(—Z—R)₂.

In a fourth aspect of the invention, there is provided method forproducing a polyester, comprising contacting an anhydride and an epoxidewith a catalyst system having a catalyst of formula (IA):

wherein

R₁ and R₂ are independently hydrogen, halide, a nitro group, a nitrilegroup, an imine, an amine, an ether group, a silyl ether group, athioether group, a sulfoxide group, a sulfinate group, or an acetylidegroup or an optionally substituted alkyl, alkenyl, alkynyl, haloalkyl,aryl, heteroaryl, alicyclic or heteroalicyclic;

R₃ is optionally substituted alkylene, alkenylene, alkynylene,heteroalkylene, heteroalkenylene, heteroalkynylene, arylene,heteroarylene or cycloalkylene, wherein alkylene, alkenylene,alkynylene, heteroalkylene, heteroalkenylene and heteroalkynylene mayoptionally be interrupted by aryl, heteroaryl, alicyclic orheteroalicyclic;

R₄ is H, or optionally substituted aliphatic, heteroaliphatic,alicyclic, heteroalicyclic, aryl, heteroaryl, alkylheteroaryl oralkylaryl;

R₅ is H, or optionally substituted aliphatic, heteroaliphatic,alicyclic, heteroalicyclic, aryl, heteroaryl, alkylheteroaryl oralkylaryl;

E₁ is C, E₂ is O, S or NH or E₁ is N and E₂ is O;

Z is absent, or is selected from -E-, -EX(E)-, or -EX(E)E-;

X is S or C;

E is —O—, —S—, or NR^(Z), wherein is H, or optionally substitutedaliphatic, heteroaliphatic, alicyclic, heteroalicyclic, aryl,heteroaryl, alkylaryl or alkylheteroaryl;

R is hydrogen, or optionally substituted aliphatic, heteroaliphatic,alicyclic, heteroalicyclic, aryl, heteroaryl, alkylaryl,alkylheteroaryl, or silyl, or a polymer; and when Z is absent, R mayadditional be selected from halide, phosphinate, azide and nitrate;

each G is independently absent or a neutral or anionic donor ligandwhich is a Lewis base; and

M is Zn(II), Cr(II), Co(II), Mn(II), Mg(II), Fe(II), Ti(II),Cr(III)-Z—R, Co(III)-Z—R, Mn (III)-Z—R, Fe(III)-Z—R, Ca(II), Ge(II),Al(III)-Z—R, Ti(III)-Z—R, V(III)-Z—R, Ge(IV)-(—Z—R)₂ or Ti(IV)-(—Z—R)₂.

The preferred embodiments of the complex of formula (IA) described inthe first aspect apply equally to the second, third and fourth aspects.

The preferred embodiments of the compound [Y] as described in the firstaspect apply equally to the second aspect.

The methods of the first, second, third and fourth aspects may becarried out in the presence of a solvent. Examples of solvents useful inthe first, second, third and fourth aspects include toluene, diethylcarbonate, dimethyl carbonate, dioxane, dichlorobenzene, methylenechloride, propylene carbonate, ethylene carbonate, etc.

In each of the methods of the first, second, third and fourth aspects,the catalyst system may comprise a chain transfer agent.

The chain transfer agent may be any chain transfer agent as defined inWO 2013/034750, the entire contents of which are hereby incorporated byreference. Exemplary chain transfer agents include water, an amine, analcohol, a thiol, a phosphinate and a carboxylic acid.

The chain transfer agent may be present in a molar ratio of at least 1:1relative to the metal complex (catalyst of formula (I)). For example,the chain transfer agent is present in a molar ratio of at least 2:1, atleast 4:1, at least 8:1, at least 16:1, at least 32:1 or at least 64:1relative to the metal complex.

The chain transfer agent may be used to control the molecular weight(M_(n)) of the polymers produced by the process of the first, second,third and fourth aspects. Preferably, the molecular weight (M_(n)) ofthe polymers is from about 1,000 g/mol to about 100,000 g/mol. Themolecular weight of the polymers produced can be measured by GelPermeation Chromatography (GPC) using, for example, a GPC-60manufactured by Polymer Labs, using THF as the eluent at a flow rate of1 ml/min on Mixed B columns, manufactured by Polymer Labs. Narrowmolecular weight polystyrene standards can be used to calibrate theinstrument.

The chain transfer agent may also be used to form polymers produced bythe process of first, second, third and fourth aspects which areterminated by hydroxyl groups (i.e. polyol polycarbonates/polyesters).The hydroxyl terminated polymers may be used to produce other polymericproducts, such as polyurethane.

In certain embodiments of the first, second, third and fourth aspects,the monomers (i.e. the epoxide, anhydride, lactide and/or lactone) maybe purified, for example by distillation, such as over calcium hydride,prior to being used of the methods according to the first, second, thirdand fourth aspects.

The method of the first, second third and fourth aspects of theinvention may be carried out at a temperature of about 0° C. to about200° C., for example, from about 25° C. to about 140° C., such as fromabout 50° C. to about 140° C. preferably from about 60° C. to about 100°C. The duration of the process may be up to 168 hours preferably 1 to 24hours.

The method of the first, second, third and fourth aspects of theinvention may be carried out at low catalytic loading, for example, thecatalytic loading for the process is preferably in the range of1:1,000-100,000 catalyst:monomer, more preferably in the region of1:1,000-50,000 catalyst:monomer, even more preferably in the region of1:1,1000-10,000, and most preferably in the region of 1:10,000catalyst:monomer.

The methods of the first, second, third and fourth aspects may becarried out in the presence of a gas. For example, when the inventivemethods comprise CO₂ as a reagent, the CO₂ may be present alone, or incombination with another gas, such as nitrogen. The methods may becarried out at low pressures, such as 1 atm gas (e.g. 1 atm CO₂).However, the methods may also be carried out at pressures above 1 atm,such as 40 atm gas (e.g. 40 atm CO₂).

In a fifth aspect of the invention, there is provided a polymerobtainable from the method according to the first, second, third orfourth aspects.

It will be appreciated that the various preferred features describedabove for formula (IA) may be present in combination mutatis mutandis.

BRIEF DESCRIPTION OF FIGURES

FIG. 1: ATR-IR analysis of PCL-PCHC formation, showing normalised peakintensities for absorptions at 694, 1738 and 1750 cm−1 against time/min.

FIG. 2: GPC traces of PCHPE-b-PCL and PCHPE block copolymer. Curves a-dcorrespond to entries 1-4 in Table 2, respectively.

FIG. 3: ¹H NMR spectrum (CDCl₃, 298 K) of PCHPE-PCL copolymer. The plotillustrates the formation of both POPE and PCL blocks.

FIG. 4: M_(n) and M_(w)/M_(n) vs mol % of ε-CL conversion of PCLhomopolymer catalysed by [L¹Zn₂(OAc)₂]/CHO system at 80° C.

FIG. 5: Plot of In{[LA]₀/[LA]_(t)} vs time, showing a polymerisationkinetics with a first-order dependence on lactide concentration,initiated by [L¹Mg₂OAc₂]/CHO system (cat/CHO/LA=1/10/100, 100° C.).

FIG. 6: ¹H NMR spectrum (CDCl₃, 298 K) of PCL-PCHC copolymer. The plotillustrates the formation of both PCHC and PCL blocks.

FIG. 7: ATR-IR analysis of “one-pot” reaction between phthalic anhydride(PA), cyclohexeneoxide (CHO), and carbon dioxide.

FIG. 8: ¹H NMR spectra for terpolymerization reaction using L¹Zn₂(OAc)₂Spectra show that PA is fully consumed before PCHC is formed.

FIG. 9: ¹H NMR spectrum (CDCl₃, 298 K) showing formation of PCHC in thepresence of ε-CL, with no formation of PCL (4.00 ppm) or ether linkages(3.45 ppm).

FIG. 10: ATR-IR analysis of “one-pot” reaction between phthalicanhydride (PA), cyclohexeneoxide (CHO) and caprolactone (ε-CL).

FIG. 11: ¹H NMR spectrum (CDCl₃, 298 K) showing formation of PCL in thepresence of CHO, without polymerization of CHO (absence of (poly)etherlinkage at 3.45 ppm).

FIG. 12: SEC stack plot showing the analysis of PCHC-PCL formation. The“PCHC” trace shows the analysis of an aliquot removed after 4 h, whichshowed 10% CHO conversion and PCHC formation, with M_(n) 530 g/mol. Atthis point, the CO₂ was removed leading to ε-CL ROP. After 2 h, a secondaliquot was removed showing>99% conversion of ε-CL and formation ofPCHC-PCL of M_(n) 2350 g/mol.

FIG. 13: Plot of changes in intensity of IR resonances where PCHC-PCL isformed by: 1) by ROCOP of CHO/CO₂, 2) removal of CO₂ and 3) ROP of CL.

FIG. 14: SEC trace showing the molecular weight distribution PCHC andpurified PCL-PCHC-PCL as described in Table 14, Entry 1.

FIG. 15: ¹H NMR spectrum showing the carbonate content of crudePCL-PCHC-PCL and purified PCL-PCHC-PCL.

FIG. 16: SEC trace showing the molecular weight distribution PCHC andcrude PCL-PCHC-PCL as described in Table 14, Entry 2.

FIG. 17: MALDI TOF mass spectra of PCL obtained in neat CHO in theabsence of ethylene glycol.

FIG. 18: MALDI TOF mass spectra of PCL obtained in toluene in thepresence of ethylene glycol.

EXAMPLES Example 1 Ring Opening Polymerisation of a Lactone andCopolymerisation of an Anhydride and an Epoxide

Previous studies have shown that complex 1 is an excellent catalyst forthe copolymerization of carbon dioxide and cyclohexene oxide (CHO) toyield poly(cyclohexylene carbonate) (PCHC), with a high fidelity (>95%)of carbonate repeat units. Complex 2 was selected as a pre-catalyst fromwhich a range of different catalysts could be prepared by reactionbetween the phenyl substituents and protic reagents. For example, thereaction between complex 2 and iPrOH yields the di-zinc di-i-propoxidecomplex, in situ, with release of benzene.

Complex 2 is capable of copolymerising CHO/CO₂, yielding PCHC with anequivalent TON and TOF to 1 (˜400, 20, respectively), and >99% ofcarbonate linkages in the copolymer. The copolymerization is also highlyefficient, yielding 98% polymer, with just 2% cyclohexene carbonateby-product.

Catalyst 2, in combination with four equivalents of iPrOH, is anexcellent catalyst system for caprolactone (ε-CL) ring-openingpolymerisation (ROP), producing poly(caprolactone) (PCL) with a high TON(460)/TOF (2300 h−1), as complex 2 reacts with iPrOH in situ to form[L¹Zn₂(O^(i)Pr)₂].

The PCL has an Mn of 30,000 g/mol.

In contrast, the ROP of caprolactone does not proceed at all usingcatalyst 1, when ε-CL is used alone, or in combination with iso-propylalcohol. Furthermore, exposure of the initiating system 2/^(i)PrOH andε-CL to 1 bar pressure of CO₂ completely deactivates the catalyst andprevents any ROP occurring.

Thus, it can be seen that for ε-CL ROP alkoxide groups can initiatepolymerization, whereas carbonate and carboxylate groups cannot.

Complexes 1 and 2 are also efficient catalyst for the copolymerizationof CHO and phthalic anhydride (PA), yielding the polyesterpoly(cyclohexylene phthalic)ester (PCHPE), with a high TON (1000)/TOF(50 h⁻¹) and high proportion of ester chain linkages (>99%).

TABLE 1 Performance of Catalysts 1 and 2 for Polyester and PolycarbonateFormation Time TOF^(b)) Mn^(c)) Monomers Catalyst (h) TON^(a)) (h⁻¹) (g· mol⁻¹) PDI^(c)) CHO/CO₂ ^(d)) 1 24 439 18 6200 1.19 CHO/CO₂ ^(d)) 2 20408 20 5035 1.08 ε-CL^(e)) 1 + iPrOH 24 — — — — ε-CL^(e)) 2 + iPrOH 0.2460 2300 30,000 1.47 (92%) ^(a))Turn-over-number (TON) = moles monomerconsumed/moles catalyst added, where moles monomer consumed isdetermined from the % conversion observed in the ¹H NMR spectrum of thecrude polymer, ^(b))Turn-over-frequency (TOF) = TON/time (h),^(c))Determined by size exclusion chromatography, calibrated againstnarrow Mw Polystyrene standards (see ESI). ^(d))Polymerization conductedat 80° C., 1 bar CO₂ pressure, 0.1 mole % catalyst in neat CHO.^(e))Polymerization conducted at 80° C., 0.2 mole % catalyst, 0.8 mole %iPrOH (4 eq.) in neat ε-CL. f) Polymerization conducted at 100° C., 0.1mole % catalyst in 1:9 mixture of pthalic anhydride:cyclohexene oxide,g) based on PA conversion.

The PCHPE has an M_(n) of 4000 g/mol, and a narrow PDI (1.33).

Example 2 Preparing a poly(caprolactone-co-cyclohexylene carbonate)Block Copolymer by Sequential Monomer Addition

Reacting complex 2 (as set out in Example 1), with 4 eq. iPrOH, resultsin a catalyst having a zinc alkoxide propagating species. ε-CL dissolvedin CHO is exposed to this catalyst system, resulting in formation ofPCL. After 120 minutes, 1 bar pressure of CO₂ is added to thepolymerization system.

FIG. 1 illustrates the ATR-IR analysis of the polymerization. Initially,ε-CL is polymerized; this can be observed the sharp decrease inintensity of the absorptions at 694 and 1750 cm−1 (inset FIG. 1) due toε-CL. The complete consumption of ε-CL occurs over just 20 minutes.After 120 minutes, (>5 half-life), 1 bar pressure of CO₂ is added to thepolymerization system. The ATR-IR analysis shows the immediate formationof polycarbonate, as observed by the increasing intensity of signals at1750 and 1738 cm⁻¹.

The polymerization was stopped after 24 h, the only product waspoly(caprolactone-co-cyclohexylene carbonate) PCL-PCHC by GPC. The TONand TOF for the carbonate block formation are 460 and 23 h⁻¹,respectively and the carbonate block shows a very high fidelity ofcarbonate repeat units(>99%).

The block copolymer has Mn of 5170 g/mol, PDI=1.27. Analysis of theintegrals for the PCHC vs PCL blocks, in the ¹H NMR spectrum, shows anapproximate composition of 3:1, PCHC:PCL, which matches well with thecomposition predicted on the basis of stoichiometry (3.5:1).

Example 3 Preparing a poly(caprolactone-co-cyclohexylene carbonate)Block Copolymer by Sequential Monomer Addition

Cyclohexene oxide (2.2 mL, 21.5 mmol), ε-caprolactone (277 μL, 2.5 mmol)and complex 1 (20 mg, 25.0 μmol) were added to a Schlenk tube. Thevessel was heated at 353 K, under N₂, for 1 h then de-gassed and 1 barof CO₂ was added. The vessel was heated for 20 h. A sample of the crudeproduct was analysed by ¹H NMR spectroscopy to determine the conversionand selectivity. Any unreacted monomers were removed, in vacuo, to yieldthe product as a white powder. M_(n)=4,810, PDI=1.28.

Example 4 Production of Di-Block and Tri-Block Copolymers

It can be seen from Example 2 that catalyst 2 can selectively polymerizeε-CL, in the presence of CHO, to produce PCL with good control of theM_(n). Removal of an aliquot from the polymerization after 120 mins,shows complete consumption of the ε-CL monomer and formation of PCL ofM_(n) 6950 g/mol (PDI: 1.51).

The zinc-alkoxide polymer chain end can be further reacted with 50 eq.of phthalic anhydride (vs. 800 equivalents of CHO) to produce a blockcopolyester (PCL-CHPE). Removal of an aliquot from the reaction mixtureafter 400 mins shows the complete consumption of PA has occurredyielding a diblock copolyester with M_(n) 7360 g/mol (PDI: 1.62). Usingan excess of CHO ensures that the growing polymer chain end is a zincalkoxide species (vs. a zinc carboxylate which would be formed if excessPA were applied). This zinc alkoxide species was reacted with a further200 equivalents of ε-CL to produce an ABA type triblock copolyester(PCL-PCHPE-PCL). The triblock copolymer has an Mn 12680 g/mol (PDI:1.70).

An ABC type block copolyester carbonate is produced by reacting ε-CLwith catalyst 2/iPrOH catalyst system, in CHO, to produce a zincalkoxide chain terminated PCL dissolved in CHO. This PCL is then reactedwith 50 eq. of PA, and the zinc alkoxide species initiates thecopolymerization of CHO and PA. Because CHO is present in excess and thereaction is run to complete consumption of PA, the growing polymer chainis terminated by a zinc alkoxide species. The diblock polymer is thenexposed to 1 bar pressure of carbon dioxide, and the copolymerization ofcarbon dioxide and CHO progresses to form a PCL-PCHPE-PCHC, an ABC typecopolymer.

Example 5 Production of Di-Block Using Complex 1

Complex 1 (10.0 mg, 1.25×10⁻² mmol), phthalic anhydride (37.0 mg, 0.25mmol) and ε-CL (210.0 μL, 1.88 mmol) were dissolved in CHO (505.0 μL,5.00 mmol) under N₂ protection in a screw vial charged with a stir bar.The mixture was then heated to 100° C. and left to react under inertatmosphere for 2 h. The relative molar ratio of [Zinccat.]/[CHO]/[PA]/[ε-CL] were as described in Table 2. The obtained blockcopolymers were precipitated using cold MeOH.

TABLE 2 Synthesis of PCHPE-b-PCL from a mixed monomer feedstock of CHO,PA and ε-CL. Entry [cat.]/[CHO]/[PA]/[ε-CL] TOF of PA (h⁻¹) M_(n) (kDa)M_(w)/M_(n) 1 1/500/20/100 ~13 12.2 1.42 2 1/500/20/150 ~13 15.8 1.43 31/500/20/200 ~13 18.7 1.57 4 1/500/10/150 ~10 22.5 1.46 5 1/500/40/150~14 28.0 1.52 3.9 1.03

FIG. 2 shows GPC traces of PCHPE-b-PCL and PCHPE blocks. Curves a-dcorrespond to entries 1-4 in Table 2, respectively.

FIG. 3 shows ¹H NMR spectrum (CDCl₃, 298 K) of the PCHPE-PCL copolymer.The plot illustrates the formation of both PCHPE and PCL blocks.

Example 6 Ring Opening of Cyclic Esters

The following reactions demonstrate the ring opening of lactides andlactones using the catalysts of the invention.

TABLE 3 Polyester formation via ROP of cyclic esters. Mn^(b) Mono-cat./^(i)PA/ T Time Conv.^(a) (g · X mer M (° C.) (h) (%) mol⁻¹) PDI^(b)OAc ε-CL 1/4/500 80 2 h 30 0 — — OAc rac-LA 1/4/500 80 24 h 0 — — C₆H₅ε-CL^(c) 1/4/500 80 <10 mn 91.7 29970 1.47 C₆H₅ ε-CL 1/4/500 r.t. 23h^(e) >99 41480 1.40 C₆H₅ rac-LA^(d) 1/4/200 80 15 h^(e) >99 12585 1.30C₆H₅ rac-LA 1/4/200 r.t. 2 h 96.6 11125 1.16 C₆H₅ rac-LA 1/-/200 r.t. 2h 92.6 28185 1.49 Reaction conditions: [M]₀ = 1M, DCM as solvent;^(a)Determined by ¹H NMR spectroscopy; ^(b)Determined by GPC withpolystyrene standards; ^(c)neat, ε-CL as solvent; ^(d)toluene assolvent; ^(e)non-optimized time.

Example 7 Ring Opening of Cyclic Esters Initiated by Complex 1/EpoxideSystem

The following reactions demonstrate the ring opening of lactides andlactones using the catalysts of the invention in the presence ofepoxide.

i. Controlled Polymerization of ε-CL Initiated by Complex1/EpoxideSystem

Cyclohexene oxide (2.55 mL, 25 mmol), ε-caprolactone (0.831 mL, 7.5mmol) and L¹Zn₂OAc₂ (10 mg, 0.0125 mmol) were added to a Schlenk tube.The vessel was heated at 80° C. as described in Table 4. The unreactedmonomers were removed in vacuo.

TABLE 4 Polyester formation via ROP of cyclic esters Time Conv.^(a)Mn^(b) (min) (%) (g · mol⁻¹) PDI^(b) 20 9.8 6,000 1.23 30 26.5 17,5001.25 34 33.3 19,100 1.19 38 53.8 35,900 1.28 42 66.5 44,500 1.38 46 8659,000 1.33 56 93.0 65,600 1.34 Reaction conditions: Mixed monomer assolvent, 80° C., L¹Zn₂(OAc)₂ as catalyst, cat/CHO/eCL = 1/2000/600;^(a)Conversion of monomer determined by ¹H NMR spectroscopy;^(b)Experimental M_(n) determined by GPC in THF, using polystyrenestandards and times correction factor 0.54 for PLA to determine absolutemolecular weight.

FIG. 4 shows M_(n) and M_(w)/M_(n) vs mol % of ε-CL conversion of PCLhomopolymer catalyzed by [L¹Zn₂(OAc)₂]/CHO system at 80° C.

ii. Variation of Ratio Catalyst/Epoxide for ε-CL ROP.

L¹Zn₂OAc₂ (15 mg, 0.0188 mmol), cyclohexene oxide, ε-caprolactone andtoluene were added to a Schlenk tube (molar ratio cat/CHO/ε-CL asdescribed in Table 5). The vessel was heated at 80° C. as described inTable 5. The unreacted monomers were removed in vacuo.

TABLE 5 eCL polymerisation initiated by catalyst/epoxide systemscat./CHO/ Temp. Time Conv^(a) M_(n) ^(b) Cat eCL (° C.) Conc. (h) (%)(g/mol) PDI^(d) L¹Zn₂OAc₂ 1/0/100 80 1M 5 0 — — L¹Zn₂OAc₂ 1/5/100 80 1M5 88 11500 1.41 L¹Zn₂OAc₂ 1/10/100 80 1M 5 86 10500 1.25 L¹Zn₂OAc₂1/20/100 80 1M 5 88 8300 1.36 L¹Zn₂OAc₂ 1/50/100 80 1M 5 87 7300 1.31L¹Mg₂OAc₂ 1/10/100 80 1M 5 100 8150 1.25 L¹Mg₂OAc₂ 1/20/100 80 1M 5 1006300 1.66 L¹Mg₂OAc₂ 1/50/100 80 1M 5 93 4500 1.41 ^(a)Conversion ofmonomer determined by ¹H NMR spectroscopy; ^(b)Experimental M_(n)determined by GPC in THF, using polystyrene standards and timescorrection factor 0.56 for eCL to determine absolute molecular weight;^(c)Calculated M_(n) value obtained from the relation [eCL]/[cat.] ×conv × 114/2 (Assuming two polymer chains formed per catalyst);^(d)M_(w)/M_(n); ^(e)Calculated M_(n) value obtained from the relation[eCL]/[cat.] × conv × 114

iii. Polymerization of Rac-Lactide Initiated by Catalyst/Epoxide Systems

L¹Zn₂OAc₂ (15 mg, 0.0188 mmol), cyclohexene oxide, rac-lactide andtoluene were added to a Schlenk tube (molar ratio cat/CHO/LA asdescribed in Table 6). The vessel was heated at 80° C. as described inTable 6. The unreacted monomers were removed in vacuo.

TABLE 6 Polymerization of rac-lactide initiated by catalyst/epoxidesystems cat./CHO/ Temp. Time Conv^(a) M_(n) ^(b) Cat. LA (° C.) Conc.(h) (%) (g/mol) PDI^(d) L¹Zn₂OAc₂ 1/10/100 80 1M 5 31 3700 1.26L¹Zn₂OAc₂ 1/10/100 100 1M 5 97 4100 2.07 L¹Zn₂OAc₂ 1/0/100 100 1M 5 0 —— L¹Zn₂OAc₂ 1/1/100 100 1M 5 3.4 210 1.21 L¹Zn₂OAc₂ 1/2/100 100 1M 5 251150 1.20 L¹Zn₂OAc₂ 1/5/100 100 1M 5 44 3500 1.25 L¹Zn₂OAc₂ 1/20/100 1001M 5 98 6900 1.33 L¹Mg₂OAc₂ 1/2/100 100 1M 2 6 260 1.00 L¹Mg₂OAc₂1/5/100 100 1M 2 91 2800 1.95 L¹Mg₂OAc₂ 1/20/100 100 1M 2 98 3100 1.80L¹Mg₂OAc₂ 1/50/100 100 1M 2 78 2400 1.29 ^(a)Conversion of monomerdetermined by ¹H NMR spectroscopy; ^(b)Experimental M_(n) determined byGPC in THF, using polystyrene standards and times correction factor 0.58for LA to determine absolute molecular weight; ^(c) M_(w)/M_(n.)

FIG. 5 features a plot of In{[LA]₀/[LA]_(t)} vs time showing apolymerisation kinetics with a first-order dependence on lactideconcentration, initiated by L¹Mg₂OAc₂/CHO system (cat/CHO/LA=1/10/100,100° C.).

Example 8 Copolymerisation of and Epoxide and an Anhydride

The following reactions demonstrate the copolymerisation of and epoxideand an anhydride using the catalysts of the invention.

TABLE 7 Polyester synthesis via CHO/anhydride copolymerization.CHO/anhydrie T Time Conv. % Mn^(c) Catalyst (eq./eq.) Solvent (° C.) (h)(%)^(a,b) polyesters^(b) (g/mol) PDI^(c) L¹Zn₂(OAc)₂ CHO/MA Toluene 10018 92 67 12700, 1.09, 100/100 [M]₀ = 2.4M 4330 1.03 L¹Zn₂(OAc)₂ CHO/PAToluene 100 22 27 90 5100, 1.07 100/100 [M]₀ = 1.25M 2000 1.07L¹Zn₂(OAc)₂ CHO/PA neat 100  20^(d) >99^(e)  >99 4000 1.33 800/100L¹Mg₂(OAc)₂ CHO/PA neat 100  6 52 88 800/100 L¹Mg₂(OAc)₂ CHO/PA Toluene100/100 [M]₀ = 2.5M 100 22 19 83 2570 1.20 L¹Mg₂(OAc)₂ CHO/PA neat 100 1  97^(e) >99 12670, 800/100 5470 ^(a)Determined by ¹H NMRspectroscopy; ^(b)Estimated on CHO consumption, ^(c)Determined by GPCwith polystyrene standards; ^(d)Non-optimized time; ^(e)Estimated on PAconsumption.

TABLE 8 Polyester synthesis via styrene oxide (SO)/anhydridecopolymerization. SO/ % anhydrie Time Conv. poly- Mn^(c) Catalyst(eq./eq.) (h) (%)^(a,b) mer^(b) (g/mol) PDI^(c) L¹Zn₂(OAc)₂ SO/MA16^(d) >95 81 3400 1.90 200/200 L¹Zn₂(OAc)₂ SO/MA  6^(e) >95 74 29801.51 500/500 L¹Zn₂(OAc)₂ SO/PA 22^(d) >95 77 2340 1.49 200/200 Reactionconditions: reaction in toluene, 100° C., [M]₀ = 2.5M, ^(a)Determined by¹H NMR spectroscopy; ^(b)Estimated on SO consumption, ^(c)Determined byGPC with polystyrene standards; ^(d)Non-optimized time; ^(e)Monitored byATR-IR.

Example 9 Synthesis of Polyester-Polycarbonate Block Polymers

PCL-PCHC

TABLE 9 PCL-PCHC via step polymerization procedure. ε-CL CHO ε-CL/ CatCo-cat t₁ conv. t₂ conv. TOF CHO (eq.) (eq.) (h) (%)^(a) (h) (%)^(a) TON(h⁻¹) 500/500 2 iPA 0.5 94 20 23.2 115 5.8 (4 eq) 100/900 2 iPA 3 94 1634.4 310 19.4 (4 eq) 100/90 2 iPA 2 93 16 66.5 698 37.4 (4 eq) 100/900 2iPA 2 — 20 51.3 461 23.1 (4 eq) 100/900 1 — 1 >99  21 53 477 22.7Reaction conditions: L¹Zn₂Ph₂ (1 eq.) in the presence of iPA (4 eq.),80° C., desired time, neat (monomer mix as solvent), ^(a)Determined by¹H NMR spectroscopy.

FIG. 6: ¹H NMR spectrum (CDCl₃, 298 K) of PCL-PCHC copolymer. The plotillustrates the formation of both PCHC and PCL blocks when initiated bycat 1 (Table 9, entry 5).

TABLE 10 PCL-b-PCHC bloc polymer characterization. Mn^(a) % Mn^(a) %E-CL/ (g · poly- (g · poly- CHO mol⁻¹) PDI^(a) carbonate^(b) mol⁻¹)PDI^(a) carbonate^(b) 500/500 20782 1.43 8.6 100/900 4808 1.65 57 75721.16 30.5 100/900 4355 1.34 71 100/900 5170 1.27 76 100/900 4810 1.38 74^(a)Determined by GPC with polystyrene standards, ^(b)Determined by ¹HNMR spectroscopy by comparison of PCL and PCHC signals, respectively.

PE-PCHC (“One-Pot” Procedure)

TABLE 11 Polyester-polycarbonate bloc polymers obtained via one-potpolymerization procedure. ε-CL/ CHO % % CHO t conv. poly- poly- TOF(eq.) (h) (%)^(a) mer^(a) carbonate^(a) TON (h⁻¹) Mn^(b) PDI^(b) 100/90021.8 15 81 75 134 6.1 3965 1.33 200/2000 22.2 18 91 96 362 16.5 42901.12 Reaction conditions: L¹Zn₂(OAc)₂ (1 eq.), 1 atm CO₂, 100° C.,desired time, neat (CHO as solvent), ^(a)Determined by ¹H NMRspectroscopy, ^(b)Determined by GPC with polystyrene standards.

The second reaction in Table 11 was monitored by ATR-IR spectroscopy(see FIG. 7). FIG. 7 shows that anhydride is consumed as the polyesterfirst block is produced.

Polyester formation terminates and polycarbonate second block formationbegins once all anhydride monomer has been consumed.

FIG. 8 features ¹H NMR spectra for the terpolymerization reaction usingthe complex L¹Zn₂(OAc)₂ Reaction conditions: 1:100:800. Cat:PA:CHO, 100°C. under 1 bar CO₂. Spectra show that PA is fully consumed before PCHCis formed. Thus, aliquot after 4 h shows almost complete consumption ofPA (by 1H NMR spectroscopy) and no formation of PCHC. At the end of thereaction (24 h), aliquot show formation of PCHC.

Example 9 Preparation Polymers from Epoxide, Carbon Dioxide, Anhydrideand Lactone Monomers

TABLE 12 Polyester, polycarbonate and polycarbonate-polyester blockcopolymers obtained via one-pot polymerization procedure T t Conv. MnCHO ε-CL CO₂ PA (° C.) (h) (%) (g/mol) PDI 900 100 1 atm. — 80 15 h 12.41040 1.08 400 200 — 50 100 10 h Full 8140 2.00 20 200 — — 80  2 h Full21040 1.41

Formation of PCHC in the presence of ε-CL: Cyclohexene oxide (1.1 mL,10.75 mmol), ε-caprolactone (138.6 μL, 1.2 mmol) and L¹Zn₂OAc₂ (10 mg,0.012 mmol) were added to a Schlenk tube. The vessel was degassed thenCO₂ was added and let under stirring for 30 mn at r.t. The vessel wasthen heated at 80° C. under CO₂ atmosphere (1 atm.) for 15h. Theunreacted monomers were removed in vacuo (Mn=1040 g/mol, PDI=1.08).

FIG. 9: ¹H NMR spectrum (CDCl₃, 298 K) showing formation of PCHC in thepresence of ε-CL, with no formation of PCL (4.00 ppm) or ether linkages(3.45 ppm) (Table 12, Entry 1).

PCHPE-PCL formation: Cyclohexene oxide (1 mL, 10.0 mmol), ε-caprolactone(554 μL, 5.0 mmol), phtallic anhydride (185.2 mg, 0.625 mmol) andL¹Zn₂OAc₂ (20 mg, 0.025 mmol) were added to a Schlenk tube. The vesselwas heated at 100° C. under stirring for 10 h (monitored by ATR-IR). Theunreacted monomers were removed in vacuo (Mn=8140 g/mol, PDI=2.00).

FIG. 10 shows an ATR-IR trace for PCHPE-PCL formation. This figure showsthat the anhydride is consumed as the polyester block forms. When all ofthe anhydride is consumed, ring opening of the lactone occurs.

PCL formation (in the presence of 10 mol % of CHO): Cyclohexene oxide(25 μL, 0.25 mmol), ε-caprolactone (277 μL, 2.5 mmol) and L¹Zn₂OAc₂ (10mg, 0.0125 mmol) were added to a Schlenk tube. The vessel was heated at80° C. under stirring for 2 h. The unreacted monomers were removed invacuo (Mn=21040 g/mol, PDI=1.41).

FIG. 11 is a ¹H NMR spectrum (CDCl₃, 298 K) showing formation of PCL inthe presence of CHO, without polymerization of CHO (absence of(poly)ether linkage at 3.45 ppm).

Example 10 Preparing a poly(cyclohexylene carbonate-co-caprolactone)Block Copolymer by Sequential Monomer Addition

-   -   A) Cyclohexene oxide (2.3 mL, 22.5 mmol), ε-caprolactone (277        μL, 2.5 mmol), and 1 (40 mg, 50.0 μmol) were added to a Schlenk        tube. The vessel was degassed at 298 K, then CO₂ was added. The        vessel was left under a CO₂ atmosphere, at 298 K, for a few        minutes and was then heated to 353 K, with continuous reaction        stirring, for 3.5 h. Then, the CO₂ was removed from the reaction        via 6 vacuum-nitrogen cycles, over a period of 15 min. The        vessel was maintained at 353 K for 3 h. A sample of the crude        product was analysed by ¹H NMR spectroscopy to determine the        conversion and selectivity. Any unreacted monomers were removed,        in vacuo, to yield the product as an oily white wax. M_(n)=3,490        g/mol, PDI=1.48.    -   B) Cyclohexene oxide (2.3 mL, 22.5 mmol), ε-caprolactone (277        μL, 2.5 mmol), and 1 (40 mg, 50.0 μmol) were added to a Schlenk        tube. The vessel was degassed at 298 K, then CO₂ was added. The        vessel was left under a CO₂ atmosphere, at 298 K, for a few        minutes and was then heated to 353 K, with continuous reaction        stirring, for 4 h. Then, the CO₂ was removed from the reaction        via 6 vacuum-nitrogen cycles, over a period of 15 min. The        vessel was maintained at 353 K for 2 h. A sample of the crude        product was analysed by ¹H NMR spectroscopy to determine the        conversion and selectivity. Any unreacted monomers were removed,        in vacuo, to yield the product as an oily white wax. M_(n)=2,349        g/mol, PDI=1.49.

FIG. 12 features a SEC stack plot showing the analysis of PCHC-PCLformation according to the conditions described in example 10-B. The“PCHC” trace shows the analysis of an aliquot removed after 4 h, whichshowed 10% CHO conversion and PCHC formation, with M_(n) 530 g/mol. Atthis point, the CO₂ was removed leading to CL ROP. After 2 h, a secondaliquot was removed was >99% conversion of CL and formation of PCHC-PCLof M_(n) 2350 g/mol.

FIG. 13 shows changes in intensity of IR resonances where PCHC-PCL isformed by: 1) by ROCOP (ring opening copolymerisation) of CHO/CO₂, 2)removal of CO₂ and 3) ROP of CL.

Example 9 Use of Various Epoxides as Switch Reagent for PCL Production

LZn₂(OAc)₂ (1 eq), ε-caprolactone (200 eq), and epoxide (800 eq) wereadded to a schlenk tube. The mixture was heated to 80° C. for 3 hours.After 3 hours a NMR aliquot was taken to determine conversion and theexcess epoxide was removed by vacuum. The polymer was precipitated fromTHF by methanol.

TABLE 13 Ring-opening polymerization of ε-CL initiated by acatalyst/epoxide system^(a) Conversion^(a) Mn^(b) Cat/Epoxide/e-CLEpoxide Solvent (%) (g/mol) PDI^(b) 1/800/200 SO Neat^(c) 99 5336 1.281/800/200 VCHO Neat^(c) 90 9486 1.4 1/10/100 SO Toluene 99 21040 1.6[e-CL] = 1M 1/10/100 VCHO Toluene 90 13470 1.5 [e-CL] = 1M ^(a)Reactionconditions: 80° C., 3 hr; ^(b)Determined by ¹H NMR spectroscopy;^(c)Determined by GPC calibrated with polystyrene standards; ^(c)Mixedepoxide used as solvent. VCHO = 4-vinylcyclohexene oxide; SO = styreneoxide.

Example 10 Formation of Triblock PCL-PCHC-PCL

L¹Zn₂(TFA)₂ and CHO were added to a Schlenk tube. The cyclohexene oxidewas degassed before being left to stir under 1 atm of CO₂ at 80° C. for16 h. The carbon dioxide was removed and replaced with nitrogen. Toluenewas added to dissolve the PCHC, the desired quantity of ε-caprolactonewas then added. Upon completion, the solvent was removed by vacuum andthe polymer precipitated from THF by the addition of excess methanol.

TABLE 14 Formation of triblock PCL-PCHC-PCL Conversion^(b) Mn (PDI)^(c)CHO ε-CL (%) (g/mol) Entry (eq.) (eq.) [ε-CL]^(a) CHO ε-CL PCHCPCL-PCHC-PCL^(d) 1 1000 400 5 32 100 7,697 (1.12) 22,165 (1.78)  29,313(1.53)^(e) 2 1000 400 1 36 87 5,644 (1.09) 15,000 (1.28) Reactionconditions: i): L¹Zn₂(TFA)₂, 18 h, 1 atm CO₂, 80° C.; ii): addition oftoluene and ε-CL, 3 h, N₂ ^(a)Concentration of ε-CL in toluene;^(b)Determined by ¹H NMR spectroscopy; ^(c)Determined by GPC calibratedwith polystyrene standards, ^(d)Crude polymer before purification,^(e)after purification THF/methanol. TFA = trifuoroacetate (OCOCF₃).

FIG. 14 shows an SEC trace showing the molecular weight distributionPCHC and purified PCL-PCHC-PCL as described in Table 14, Entry 1.

FIG. 15 shows the ¹H NMR spectrum showing the carbonate content of crudePCL-PCHC-PCL and purified PCL-PCHC-PCL. There is no significantdifference in relative intensities (carbonate content) consistent withblock copolymer formation.

FIG. 16 shows an SEC trace showing the molecular weight distributionPCHC and crude PCL-PCHC-PCL as described in Table 14, Entry 2.

Example 11 ε-CL Polymerization in the Presence of Chain Transfer Agent(CTA)

e-CL polymerization with CHO as solvent in the presence of ethyleneglycol (EG): Catalyst, cyclohexene oxide (1000 eq), ε-caprolactone (200eq) and ethylene glycol (10 eq) were added to a Schlenk tube. Themixture was heated to 80° C. for 2 hours and then, the excesscyclohexene oxide was removed by vacuum. The polymer was precipitatedfrom THF by methanol.

e-CL polymerization with toluene as solvent in the presence of ethyleneglycol (EG): Catalyst, cyclohexene oxide (40 eq), ε-caprolactone (400eq), ethylene glycol (30 eq) and toluene were added to a Schlenk tube.The mixture was heated to 80° C. for 2 hours. After 2 hours the excesscyclohexene oxide removed by vacuum. The polymer was precipitated fromTHF by methanol.

TABLE 15 Polymerization of e-CL in the presence of CTA. ε-CL CHO EG[e-CL]^(a) Conv.^(b) Entry (eq.) (eq.) (eq.) (mol/L) (%) M_(n(exp)) ^(c)PDI^(c) P10 100 1000 — — 100 2779 1.36 P14 200 1000 10 — 100 4272 1.26P17 400 20 10 5 100 4319 1.30 P24 200 1000 30 — 100 9069 1.35 P29 400 1030 5 93 2754 1.18 Reaction conditions: 80° C., 2 h; ^(a)concentration ofε-CL in toluene; ^(b)Determined by ¹H NMR spectroscopy; d) determined byGPC calibrated with polystyrene standards.

FIG. 17 shows a MALDI TOF mass spectra of PCL obtained in neat CHO inthe absence of EG (Table 15, P10). Polyol series calculated for[(C₆H₁₀O₂)_(n)+C₆H₁₂O₂+K]⁺=[(114.07)_(n)+116.16+39.1]⁺

FIG. 18 shows a MALDI TOF mass spectra of PCL obtained in toluene in thepresence of EG (Table 15, P29). Square series calculated for[(C₆H₁₀O₂)_(n)+C₂H₆O₂+K]⁺=[(114.07)_(n)+63.04+39.1]⁺; circular seriescalculated for [(C₆H₁₀O₂)_(n)+C₆H₁₂O₂+K]⁺=[(114.07)_(n)+116.16+39.1]⁺.

1. A method for producing a block copolymer, using a single catalyticsystem, wherein the single catalytic system comprises a catalyst offormula (I):

Wherein: [M] is a metal complex having at least one metal atom Mcoordinated by a ligand system; M is Zn, Cr, Co, Mn, Mg, Fe, Ti, Ca, Ge,Al, Mo, W, Ru, Ni or V; Z is absent, or is independently selected from-E-, -EX(E)-, or -EX(E)E-, X is C or S; each E is independently selectedfrom O, S or NR^(Z), wherein R^(Z) is H, or optionally substitutedaliphatic, heteroaliphatic, alicyclic, heteroalicyclic, aryl,heteroaryl, alkylaryl or alkylheteroaryl; R is hydrogen, or optionallysubstituted aliphatic, heteroaliphatic, alicyclic, heteroalicyclic,aryl, heteroaryl, alkylaryl, alkylheteroaryl, silyl or a polymer; andwhen Z is absent, R may additionally be selected from halide, nitro,azide and phosphinate; the method comprising the steps of: a) forming afirst block by polymerising a first monomer or combination of monomersselected from the groups (i) to (iii): Group (i): a lactide and/or alactone, Group (ii): an epoxide and an anhydride, or Group (iii): anepoxide and carbon dioxide, b) optionally contacting the catalyst offormula (I) with a compound [Y] which is capable converting the group—Z—R, wherein Z is absent or a group selected from -E-X(E)- or-E-X(E)E-, to a group —Z—R wherein Z is -E-; c) forming a second blockby polymerising a second monomer or combination of monomers selectedfrom a different group (i) to (iii) to that selected for the firstmonomer or combination of monomers: Group (i): a lactide and/or alactone, Group (ii): an epoxide and an anhydride, or Group (iii): anepoxide and carbon dioxide, wherein when the first monomer orcombination of monomers is Group (i), Z is -E-; and wherein when thefirst monomer or combination of monomers is group (ii) or Group (iii),and the second monomer or combination of monomers is Group (i), step b)is performed after step a).
 2. The method according to claim 1, whereinthe first monomer or combination of monomers is Group (i), and Z—R is-E-R, the second monomer or combination of monomers is Group (ii) orGroup (iii) and the second monomer or combination of monomers is addedto the reaction after step a) has been performed.
 3. The methodaccording to claim 1, wherein the first monomer or combination ofmonomers is Group (ii) or Group (iii), the second monomer or combinationof monomers is Group (i), and step b) is performed after step a) andbefore step c).
 4. The method according to claim 3, wherein the secondmonomer or combination of monomers is added to the reaction with thefirst monomer or combination of monomers, or after step a) has beenperformed.
 5. A method for producing a block copolymer, said blockcopolymer having a first and second block, using a single catalyticsystem, wherein the single catalytic system comprises a catalyst offormula (I):

Wherein: [M] is a metal complex having at least one metal atom Mcoordinated by a ligand system; M is Zn, Cr, Co, Mn, Mg, Fe, Ti, Ca, Ge,Al, Mo, W, Ru, Ni or V; Z is absent, or is independently selected from-E-, -EX(E)-, or -EX(E)E-; X is C or S; each E is independently selectedfrom O, S or NR^(Z), wherein R^(Z) is H, or optionally substitutedaliphatic, heteroaliphatic, alicyclic, heteroalicyclic, aryl,heteroaryl, alkylaryl or alkylheteroaryl; R is hydrogen, or optionallysubstituted aliphatic, heteroaliphatic, alicyclic, heteroalicyclic,aryl, heteroaryl, alkylaryl, alkylheteroaryl, silyl or a polymer; andwhen Z is absent, R may additionally be selected from halide,phosphinate, azide and nitro; the method comprising the steps of: a)providing a mixture comprising: i. an epoxide; ii. a first monomer orcombination of monomers selected from a group (i) to (iii): Monomer (i):a lactide and/or a lactone, Monomer (ii): an anhydride, or Monomer(iii): carbon dioxide, and iii. a second monomer or combination ofmonomers selected from a different group (i) to (iii) to that selectedfor the first monomer or combination of monomers: Monomer (i): a lactideand/or a lactone, Monomer (ii): an anhydride, or Monomer (iii): carbondioxide; and b) contacting the mixture with the single catalytic system;wherein the rate of insertion of the first monomer or combination ofmonomers into the bond between the metal complex [M] and the ligand —Z—Ris faster than the rate of insertion of the second monomer orcombination of monomers into the bond between the metal complex [M] andthe ligand —Z—R; wherein when the first monomer or combination ofmonomers is Group (i), either —Z—R is -E-R, or the mixture comprises acompound [Y], and wherein when the second monomer or combination ofmonomers is Group (i), the mixture comprises a compound [Y].
 6. Themethod according to claim 5, wherein the mixture further comprises athird monomer or combination of monomers selected from a group which isdifferent from the first and second monomers or combination of monomers:Monomer (i): a lactide and/or a lactone, Monomer (ii): an anhydride, orMonomer (iii): carbon dioxide; wherein the rate of insertion of thefirst and second monomers are as claimed in claim 5, and wherein therate of insertion of the third monomer or combination of monomers intothe bond between the metal complex [M] and the ligand —Z—R is slowerthan the rate of insertion of the first and second monomers orcombination of monomers into the bond between the metal complex [M] andthe ligand —Z—R; and wherein when the third monomer or combination ofmonomers is Monomer (i), the reaction mixture comprises a compound [Y].7. The method according to any preceding claim, wherein the compound [Y]is a compound having a three, four or five membered saturated ring andat least one heteroatom selected from O, S or N, preferably wherein thecompound [Y] is an epoxide, an aziridine, an episulfide, an oxetane, athietane, an azetidine, a saturated furan, a saturated thiophene, apyrrolidine or a saturated four-membered carbon ring where two adjacentcarbon atoms are replaced by —Y—C(Y)—, wherein each Y is independentlyselected from O, S or NR^(Y), and wherein R^(Y) is H, or optionallysubstituted aliphatic, heteroaliphatic, alicyclic, heteroalicyclic,aryl, heteroaryl, alkylaryl or alkylheteroaryl; more preferably whereinthe compound [Y] is an epoxide.
 8. The method according to any precedingclaim, wherein the catalyst has the following formula:

wherein R₁ and R₂ are independently hydrogen, halide, a nitro group, anitrile group, an imine, an amine, an ether group, a silyl ether group,a thioether group, a sulfoxide group, a sulfinate group, or an acetylidegroup or an optionally substituted alkyl, alkenyl, alkynyl, haloalkyl,aryl, heteroaryl, alicyclic or heteroalicyclic; R₃ is optionallysubstituted alkylene, alkenylene, alkynylene, heteroalkylene,heteroalkenylene, heteroalkynylene, arylene, heteroarylene orcycloalkylene, wherein alkylene, alkenylene, alkynylene, heteroalkylene,heteroalkenylene and heteroalkynylene may optionally be interrupted byaryl, heteroaryl, alicyclic or heteroalicyclic; R₄ is H, or optionallysubstituted aliphatic, heteroaliphatic, alicyclic, heteroalicyclic,aryl, heteroaryl, alkylheteroaryl or alkylaryl; R₅ is H, or optionallysubstituted aliphatic, heteroaliphatic, alicyclic, heteroalicyclic,aryl, heteroaryl, alkylheteroaryl or alkylaryl; E₁ is C, E₂ is O, S orNH or E₁ is N and E₂ is O; Z is absent or selected from -E-, -EX(E)-, or-EX(E)E-; X is C or S; Each E is independently selected from O, S orNR^(Z), wherein R^(Z) is H, or optionally substituted aliphatic,heteroaliphatic, alicyclic, heteroalicyclic, aryl, heteroaryl, alkylarylor alkylheteroaryl; R is hydrogen, or optionally substituted aliphatic,heteroaliphatic, alicyclic, heteroalicyclic, aryl, heteroaryl,alkylaryl, alkylheteroaryl, silyl or a polymer; and when Z is absent, Rmay additionally be selected from halide, phosphinate, azide or nitro;each G is independently absent or a neutral or anionic donor ligandwhich is a Lewis base; M is Zn(II), Cr(II), Co(II), Mn(II), Mg(II),Fe(II), Ti(II), Cr(III)-Z—R, Co(III)-Z—R, Mn (III)-Z—R, Fe(III)-Z—R,Ca(II), Ge(II), Al(III)-Z—R, Ti(III)-Z—R, V(III)-Z—R, Ge(IV)-(—Z—R)₂ orTi(IV)-(—Z—R)₂.
 9. A method for producing a polyester, comprisingcontacting a lactone and/or a lactide with a catalyst system having acatalyst of formula (IA):

wherein R₁ and R₂ are independently hydrogen, halide, a nitro group, anitrile group, an imine, an amine, an ether group, a silyl ether group,a thioether group, a sulfoxide group, a sulfinate group, or an acetylidegroup or an optionally substituted alkyl, alkenyl, alkynyl, haloalkyl,aryl, heteroaryl, alicyclic or heteroalicyclic; R₃ is optionallysubstituted alkylene, alkenylene, alkynylene, heteroalkylene,heteroalkenylene, heteroalkynylene, arylene, heteroarylene orcycloalkylene, wherein alkylene, alkenylene, alkynylene, heteroalkylene,heteroalkenylene and heteroalkynylene may optionally be interrupted byaryl, heteroaryl, alicyclic or heteroalicyclic; R₄ is H, or optionallysubstituted aliphatic, heteroaliphatic, alicyclic, heteroalicyclic,aryl, heteroaryl, alkylheteroaryl or alkylaryl; R₅ is H, or optionallysubstituted aliphatic, heteroaliphatic, alicyclic, heteroalicyclic,aryl, heteroaryl, alkylheteroaryl or alkylaryl; E₁ is C, E₂ is O, S orNH or E₁ is N and E₂ is O; R is hydrogen, or optionally substitutedaliphatic, heteroaliphatic, alicyclic, heteroalicyclic, aryl,heteroaryl, alkylaryl, alkylheteroaryl, silyl or a polymer; Z is -E-; E—O—, —S—, or NR^(Z), wherein is H, or optionally substituted aliphatic,heteroaliphatic, alicyclic, heteroalicyclic, aryl, heteroaryl, alkylarylor alkylheteroaryl; each G is independently absent or a neutral oranionic donor ligand which is a Lewis base; and M is Zn(II), Cr(II),Co(II), Mn(II), Mg(II), Fe(II), Ti(II), Cr(III)-Z—R, Co(III)-Z—R, Mn(III)-Z—R, Fe(III)-Z—R, Ca(II), Ge(II), Al(III)-Z—R, Ti(III)-Z—R,V(III)-Z—R, Ge(IV)-(—Z—R)₂ or Ti(IV)-(—Z—R)₂.
 10. A method for producinga polyester, comprising contacting an anhydride and an epoxide with acatalyst system having a catalyst of formula (IA):

wherein R₁ and R₂ are independently hydrogen, halide, a nitro group, anitrile group, an imine, an amine, an ether group, a silyl ether group,a thioether group, a sulfoxide group, a sulfinate group, or an acetylidegroup or an optionally substituted alkyl, alkenyl, alkynyl, haloalkyl,aryl, heteroaryl, alicyclic or heteroalicyclic; R₃ is optionallysubstituted alkylene, alkenylene, alkynylene, heteroalkylene,heteroalkenylene, heteroalkynylene, arylene, heteroarylene orcycloalkylene, wherein alkylene, alkenylene, alkynylene, heteroalkylene,heteroalkenylene and heteroalkynylene may optionally be interrupted byaryl, heteroaryl, alicyclic or heteroalicyclic; R₄ is H, or optionallysubstituted aliphatic, heteroaliphatic, alicyclic, heteroalicyclic,aryl, heteroaryl, alkylheteroaryl or alkylaryl; R₅ is H, or optionallysubstituted aliphatic, heteroaliphatic, alicyclic, heteroalicyclic,aryl, heteroaryl, alkylheteroaryl or alkylaryl; E₁ is C, E₂ is O, S orNH or E₁ is N and E₂ is O; Z is absent, or is selected from -E-,-EX(E)-, or -EX(E)E-; X is C or S; E is —O—, —S—, or NR^(Z), wherein isH, or optionally substituted aliphatic, heteroaliphatic, alicyclic,heteroalicyclic, aryl, heteroaryl, alkylaryl or alkylheteroaryl; R ishydrogen, or optionally substituted aliphatic, heteroaliphatic,alicyclic, heteroalicyclic, aryl, heteroaryl, alkylaryl,alkylheteroaryl, or a polymer; and when Z is absent, R is additionallyselected form halide, phosphinate, azide and nitro; each G isindependently absent or a neutral or anionic donor ligand which is aLewis base; and M is Zn(II), Cr(II), Co(II), Mn(II), Mg(II), Fe(II),Ti(II), Cr(III)-Z—R, Co(III)-Z—R, Mn (III)-Z—R, Fe(III)-Z—R, Ca(II),Ge(II), Al(III)-Z—R, Ti(III)-Z—R, V(III)-Z—R, Ge(IV)-(—Z—R)₂ orTi(IV)-(—Z—R)₂.
 11. The method according to any preceding claim, whereineach E is O.
 12. The method according to any preceding claim, wherein Mis Zn or Mg.
 13. The method according to any preceding claim, whereinthe catalyst is selected from:

[L¹Mg₂Cl₂(methylimidazole)], [L₁Mg₂Cl₂(dimethylaminopyridine)],[L₁Mg₂Br₂(dimethylaminopyridine)], [L¹Zn₂(F₃CCOO)₂],[L¹Zn₂(OOCC(CH₃)₃)₂], [L¹Zn₂(OC₆H₅)₂], [L¹Fe₂Cl₄], [L¹Co₂(OAc)₃],[L¹Zn₂(adamantyl carbonate)₂], [L¹Zn₂(pentafluorobenzoate)₂],[L¹Zn₂(diphenylphosphinate)₂], [L¹Zn₂(bis(4-methoxy)phenylphosphinate)₂], [L¹Zn₂(hexanoate)₂], [L¹Zn₂(octanoate)₂],[L¹Zn₂(dodecanoate)₂], [L¹Mg₂(F₃CCOO)₂], [L¹Mg₂Br₂], [L¹Zn₂(C₆F₅)₂],[L¹Zn₂(C₆H₅)₂] and [L¹Zn₂(OiPr)₂].
 14. The method according to anypreceding claim, wherein the catalyst system comprises a chain transferagent.
 15. A polymer as produced by the method according to anypreceding claim.
 16. A method or polymer substantially as hereinbeforedescribed with reference to one or more of the examples.